CN101691448A - Antistatic thermoplastic resin composition - Google Patents
Antistatic thermoplastic resin composition Download PDFInfo
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- CN101691448A CN101691448A CN200810190850A CN200810190850A CN101691448A CN 101691448 A CN101691448 A CN 101691448A CN 200810190850 A CN200810190850 A CN 200810190850A CN 200810190850 A CN200810190850 A CN 200810190850A CN 101691448 A CN101691448 A CN 101691448A
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- thermoplastic resin
- vinyl
- alkyl
- resin composition
- antistatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0075—Antistatics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/017—Antistatic agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Abstract
An antistatic thermoplastic resin composition includes a thermoplastic resin, an anionic antistatic agent, and a conductive metal oxide. The antistatic thermoplastic resin composition has enough antistatic properties to form various shapes of product, and it is particularly applicable for the production of housings of electro-electronic products or delivery trays for manufacturing an electro-electronic product.
Description
The reference of related application
The application requires the korean patent application submitted in Korea S Department of Intellectual Property on December 31st, 2007 respectively 10-2007-0141913 number, and the right of priority of the korean patent application of submitting in Korea S Department of Intellectual Property on December 18th, 2008 10-2008-0129334 number, its whole disclosures are hereby expressly incorporated by reference.
Technical field
The present invention relates to a kind of antistatic thermoplastic resin composition.Fabulous antistatic property said composition more particularly, the present invention relates to a kind of such antistatic thermoplastic resin composition, owing to can be applicable to various goods.
Background technology
Adulterant (the mixture that comprises polycarbonate/cinnamic multipolymer, blend) be such resin compound, its processing characteristics improves and keeps high notched Izod impact strength simultaneously, and it can be applicable to the delivery tray (delivery tray) of shell as being used to make electric-electronic product of electric-electronic product or injection-molded product.Yet in order to use aforesaid resin combination, it needs antistatic property, is used to prevent owing to the infringement of static to electronic product.For the resin combination with antistatic property is provided, use static inhibitor usually, as the nitrogen compound of amine, acid amides, quaternary ammonium salt etc., or sulfonic acid, aliphatic series and aromatics sulfonium salt (salt, sulfonium salt), and aliphatic series and aromatics microcosmic salt (microcosmic salt, phosphonium salt).Yet, when independent adding static inhibitor, be difficult to realize about 10
5To 10
8The antistatic property of Ω/ (ohm-sq); In addition, can not reach the higher antistatic property that satisfies the requirement that develops as electric-electronic industry.For example, United States Patent (USP) the 5th, 500 No. 478 and the 5th, 965, has disclosed the method for preparing anti-static resin composition based on the static inhibitor of polyether ester amides by using for No. 206.Yet, be about 10 by the highest face temperature resistance that uses static inhibitor to obtain
10To 10
12Ω/.In addition, United States Patent (USP) the 5th, 010 has disclosed a kind of method of using the oxyethane base antistatic agent No. 139, but obtainable surface resistivity is up to about 10
11To 10
13Ω/, it is not enough to reach needed antistatic property in electric-electronic applications.
Summary of the invention
A kind of illustrative embodiments of the present invention provides a kind of antistatic thermoplastic resin composition with fabulous antistatic property.
Another embodiment of the invention provides a kind of layered product that utilizes antistatic thermoplastic resin composition to make (moulded product, molded product).
Embodiments of the present invention are not limited to above-mentioned technological use, and those of ordinary skill in the art can understand other technological use.
According to one embodiment of the present invention, a kind of antistatic thermoplastic resin composition is provided, it comprises thermoplastic resin, anionic antistatic agent (anionic antistaticagent) and conducting metal oxide.
According to another embodiment of the invention, provide a kind of layered product that utilizes antistatic thermoplastic resin composition to make.
Hereinafter, will describe further embodiment of the present invention in detail.
Thermoplastic resin composition according to the present invention has fabulous antistatic property, so it can be applied to various goods.Especially, its delivery tray that can be applied to be used for electric-electronic product shell or be used to make electric-electronic product.
Embodiment
Hereinafter, will describe illustrative embodiments of the present invention in detail.Yet these embodiments only are exemplary, and the present invention is not limited to this.
As employed in this article, when concrete definition was not provided, term " replacement " was meant with being selected from least one substituting group replacement in the group of being made up of halogen, C1 to C30 straight or branched alkyl, C1 to C30 haloalkyl, C3 to C30 cycloalkyl, C2 to C30 Heterocyclylalkyl, C6 to C30 aryl, C2 to C30 heteroaryl and C1 to C20 alkoxyl group.
As employed in this article, when concrete definition was not provided, term " was mixed " and is meant and comprises the heteroatoms that is selected from the group of being made up of N, O, S and P, replaced carbon atom.
Thermoplastic resin composition according to one embodiment of the present invention comprises thermoplastic resin, anionic antistatic agent and conducting metal oxide.
Hereinafter, with the exemplary composition that describes in detail among the thermoplastic resin composition who is included in according to the embodiment of the present invention.Yet these embodiments only are exemplary, and the present invention is not limited to this.
(A) thermoplastic resin
The limiting examples of thermoplastic resin comprises the graft copolymer based on vinyl, styrene base resin, rubber modified polystyrene base resin, nylon based resin of polycarbonate resin, modified rubber, based on the multipolymer of vinyl and their combination.
(A-1) polycarbonate resin
The xenol that can be by making following Chemical formula 1 and compound, halogen manthanoate (haloformate, halogen formate), carbonic ether or their combination of phosgene are reacted and are prepared polycarbonate resin.
[Chemical formula 1]
In above Chemical formula 1,
A be singly-bound, replacement or unsubstituted C1 to C5 alkylidene group, replacement or unsubstituted C1 to C5 alkylidene (alkylidene, alkylidene), replacement or unsubstituted C3 to C6 encircle alkylidene group, replacement or unsubstituted C5 to C6 and encircle alkylidene, CO, S or SO
2,
R
1And R
2Be to replace or unsubstituted C1 to C30 alkyl or replacement or unsubstituted C6 to C30 aryl independently of one another, and
n
1And n
2Be 0 to 4 integer independently of one another.
Can be used in combination the xenol represented by above Chemical formula 1 to constitute the repeating unit of polycarbonate resin.This xenol comprises quinhydrones, Resorcinol, 4,4 '-dihydroxyl phenylbenzene, 2,2-two-(4-hydroxy phenyl)-propane (being called " dihydroxyphenyl propane "), 2,4-two-(4-hydroxy phenyl)-2-methylbutane, 1,1-two-(4-hydroxy phenyl)-hexanaphthene, 2,2-two-(3-chloro-4-hydroxy phenyl)-propane, 2,2-two-(3,5-two chloro-4-hydroxy phenyls)-propane etc.In one embodiment, 2 of xenol, 2-two-(4-hydroxy phenyl)-propane, 2,2-two-(3,5-two chloro-4-hydroxy phenyls)-and propane or 1,1-two-(4-hydroxy phenyl)-hexanaphthene can be preferred, and in another embodiment, 2,2-two-(4-hydroxy phenyl)-propane can be preferred.
In one embodiment, polycarbonate resin has 10,000 to 200,000 molecular-weight average, and in another embodiment, it has the molecular-weight average of from 15,000 to 80,000 scopes, but is not limited to this.
Polycarbonate resin can be the mixture that utilizes two or more polycarbonate resins that xenol obtained that differ from one another.Polycarbonate resin can be linear polycarbonate resin, branched polycarbonate resin, polyester carbonate copolymer etc.
Linear polycarbonate resin can comprise the polycarbonate resin based on dihydroxyphenyl propane.Branched polycarbonate resin can comprise the branched polycarbonate resin by making multifunctional aromatics such as trimellitic acid 1,2-anhydride, trimellitic acid etc. and xenol and carbonate reaction and being produced.Based on the gross weight of branched polycarbonate resin, multifunctional aromatics can be comprised with the amount of 0.05mol% to 2mol%.The polyester carbonate copolymer resin can comprise the polyester carbonate copolymer resin by bifunctional carboxylic acid and xenol and carbonate reaction are produced.Carbonic ether can comprise that diaryl carbonate (diaryl carbonate) is as diphenyl carbonate and ethylene carbonate.
Based on 100 weight parts according to (A) of the present invention thermoplastic resin, can add polycarbonate resin with 45 to 100 weight parts, but in another embodiment, can add with 60 to 100 weight parts.When adding polycarbonate resin with 45 to 100 weight parts, it can provide all physical strength, shock-resistance and thermotolerance.
(A-2) graft copolymer based on vinyl of modified rubber
Can being prepared by the graft polymerization of 5 to 95wt% the monomer based on vinyl (vinyl-based monomer) of modified rubber with 5 to 95wt% rubbery polymer based on the graft copolymer of vinyl.
Monomeric limiting examples based on vinyl comprises 50 to 95wt% first monomer based on vinyl, this first monomer based on vinyl comprises the vinylbenzene that vinylbenzene that vinylbenzene, α-C1 to C4 alkyl replaces such as vinyl toluene, halogen replace, the alkyl methacrylate series that comprises C1 to C8 alkyl, the alkyl acrylate series that comprises C1 to C8 alkyl, or their combination; And 5 to 50wt% second the monomer based on vinyl, this second monomer based on vinyl comprises vinyl cyanide, methacrylonitrile, the alkyl methacrylate series that comprises C1 to C8 alkyl, the alkyl acrylate series that comprises C1 to C8 alkyl, maleic anhydride, the maleimide that C1 to C4 alkyl-or phenyl-N-replaces, or their combination.
The limiting examples of rubbery polymer comprises divinyl rubber, acryloyl rubber (acryl rubber), ethylene/propylene rubber (ethylene-propylene rubber(EPR)), styrene/butadiene rubbers, acrylonitrile/butadiene rubber, synthetic polyisoprene, ethylene-propylene-diene terpolymer (EPDM), organopolysiloxane/poly-(methyl) alkyl acrylate rubber composite (rubber composite) or their combination.
Can be used alone or in combination the graft copolymer based on vinyl of modified rubber.
Every kind of alkyl methacrylate series that comprises C1 to C8 alkyl comprises that the alkyl acrylate series of C1 to C8 alkyl is the alkyl ester of acrylic or methacrylic acid.For example, it can be available from C2 to C8 monohydroxy-alcohol.
Specific examples comprises methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate etc.In one embodiment, methyl methacrylate is preferred.
According to a kind of embodiment, the graft copolymer based on vinyl of modified rubber can comprise by with vinylbenzene, vinyl cyanide and the optional graft copolymer based on vinyl of the modified rubber that produces in divinyl rubber, acryloyl rubber or as the styrene/butadiene rubbers of mixture of (methyl) alkyl acrylate monomer graft copolymerization.
According to another kind of embodiment, the graft copolymer based on vinyl of modified rubber can comprise the graft copolymer based on vinyl by the modified rubber that the monomer-grafted copolymerization of (methyl) methyl acrylate is produced in divinyl rubber, acryloyl rubber or styrene/butadiene rubbers.
The graft copolymer based on vinyl of modified rubber can be prepared according to the known general method of those of ordinary skills, and the preparation method can comprise letex polymerization, suspension polymerization, solution polymerization or mass polymerization.According to a kind of embodiment, the preparation method can comprise letex polymerization or mass polymerization, wherein uses polymerization starter and introduce aromatic monomer based on vinyl under the situation that has rubber (rubber polymer) to exist.
Based on 100 weight parts according to (A) of the present invention thermoplastic resin, can the adding with 0 to 30 weight part of modified rubber, and in another embodiment, can adding with 0.1 to 20 weight part based on the graft copolymer of vinyl.When the graft copolymer based on vinyl of modified rubber adds fashionablely in this scope, it can provide advantage aspect shock-resistance, chemical resistant properties, processing characteristics and the cost.
(A-3) polystyrene or rubber modified polystyrene resin
Can prepare polystyrene resin by aromatic vinyl monomer according to mass polymerization, letex polymerization or solution polymerization.Aromatic vinyl monomer can comprise vinylbenzene, p-methylstyrene, alpha-methyl styrene, 4-N-propylstyrene etc.In one embodiment, vinylbenzene and alpha-methyl styrene can be preferred.
Rubber modified polystyrene resin according to the present invention is to come enrichment in addition by aromatic vinyl monomer being grafted to rubber.This rubber comprises divinyl, isoprene, 1,3-heptadiene, methyl isophthalic acid, 3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,4-pentadiene or their mixture.In one embodiment, divinyl can be preferred.Based on the total amount of rubber modified polystyrene resin, rubber can add with 5 to 15wt%.
Can prepare polystyrene or rubber modified polystyrene resin according to suspension polymerization, letex polymerization or successive polymerization.
This polystyrene or rubber modified polystyrene resin have the weight-average molecular weight of from 80,000 to 400,000 scopes.
Based on 100 weight parts according to (A) of the present invention thermoplastic resin, polystyrene or rubber modified polystyrene resin can add with 0 to 70 weight part, but in another embodiment, its scope is 0 to 50 weight part.When polystyrene or rubber modified polystyrene resin add fashionablely in 0 to 70 weight part, it can provide all shock-resistance and physical strength.
(A-4) nylon based resin
The nylon based resin can be selected from the group of being made up of following material: common known polyamide 6 (nylon 6), and it can be prepared by ring-opening polymerization lactan such as ε-Ji Neixianan and omega-lauric lactam; Nylon polymer, it can be by preparations such as amino acid such as hexosamine, the amino undecanoic acid of 11-, 12 amino dodecanoic acids; Nylon polymer, it can be by aliphatic series, alicyclic ring, or aromatic diamine such as quadrol, tetramethylene-diamine, hexamethylene-diamine, 11 methylene diamines (11 methylene diamine), dodecamethylene diamine (ten dimethylene diamines), 2,2, the 4-trimethylhexamethylenediamine, 2,4, the 4-trimethylhexamethylenediamine, 5-methyl hexamethylene-diamine in the ninth of the ten Heavenly Stems (5-methylnonahexamethylene diamine), m-xylene diamine, the p-Xylol diamines, 1,3-diamino methylcyclohexane, 1,4-diamino methylcyclohexane, 1-amino-3-aminomethyl-3,5, the 5-trimethyl-cyclohexane, two (4-aminocyclohexane) methane, two (4-methyl-4-aminocyclohexyl) methane, 2,2-two (4-aminocyclohexyl) propane, two (aminopropyl) piperazine, aminoethyl piperazine etc.; Aliphatic series, alicyclic ring or aromatics two carbonic acid such as sebacic acid, nonane diacid, terephthalic acid, methyl phosphorus phthalic acid (methyl phosphorousphthalic acid), 2-chlorine terephthalic acid, 2-methyltetraphthalic acid, 5-methyl phosphorus phthalic acid (5-methyl phosphorusphthalic acid) etc.; Their multipolymer; And their mixture.
Among them, the polymeric amide for preparing by polymerization hexanodioic acid and hexamethylene-diamine is called nylon 66.
According to a kind of embodiment, it is selected from the group of being made up of nylon 6, nylon 66 and their multipolymer.
Under the condition of 25 ℃ measurement temperature, the nylon based resin has from the relative viscosity of 2.4 to 3.8cp scopes, and wherein formic acid is 85%.When the relative viscosity of nylon based resin is in above-mentioned scope, desired physical strength such as shock-resistance can be provided, and can be applied to form a shape, so increased industrial efficiency.
The nylon based resin has from the number-average molecular weight of about 20,000 to 150,000 scopes (Mn), and amine-terminated concentration is 20 to 60mmol/kg.
Based on 100 weight parts according to (A) of the present invention thermoplastic resin, the nylon based resin can add with 0 to 70 weight part, but in another embodiment, it is in the scope of 0 to 50 weight part.When the nylon based resin adds fashionablely with 0 to 70 weight part, it can improve shock-resistance, physical strength and thermotolerance.
(A-5) based on the multipolymer of vinyl
Based on the multipolymer of vinyl by 50 to 95wt% first based on the monomer of vinyl and 5 to 50wt% second based on the monomeric copolymerization of vinyl and prepare, wherein first monomer based on vinyl comprises vinylbenzene, vinylbenzene such as alpha-methyl styrene that C1 to C4 alkyl replaces, the vinylbenzene that halogen replaces, the alkyl methacrylate series that comprises C1 to C8 alkyl, the alkyl acrylate series that comprises C1 to C8 alkyl, or their combination; And second monomer based on vinyl comprises vinyl cyanide, and methacrylonitrile comprises the alkyl methacrylate series of C1 to C8 alkyl, the alkyl acrylate series that comprises C1 to C8 alkyl, maleic anhydride, C1 to C4 alkyl-or the maleimide that replaces of phenyl N-, or their combination.
The specific examples of alkyl methacrylate series or alkyl acrylate series comprises methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, methacrylic heptyl heptylate, Octyl methacrylate, methyl acrylate, ethyl propenoate, propyl methacrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, vinylformic acid heptyl ester, Octyl acrylate etc.In one embodiment, methyl methacrylate is preferred.
When the preparation modified rubber based on the graft copolymer of vinyl the time, multipolymer based on vinyl can be used as the by product generation, and especially when the excessive monomer mixture based on vinyl is grafted to a small amount of rubbery polymer or when it comprise excessive in molecular weight regulator (control agent, during controlling agent) chain-transfer agent, can produce more based on the multipolymer of vinyl.
According to a kind of embodiment, comprise the monomer mixture of vinylbenzene, vinyl cyanide and optional methyl methacrylate based on the multipolymer of vinyl; The monomer mixture of alpha-methyl styrene, vinyl cyanide and optional methyl methacrylate; Or the monomer mixture of vinylbenzene, alpha-methyl styrene, vinyl cyanide and optional methyl methacrylate.Can prepare multipolymer according to letex polymerization, suspension polymerization, solution polymerization or mass polymerization, and it has the weight-average molecular weight of from 15,000 to 300,000 scopes based on vinyl.
According to another kind of embodiment, can be based on the multipolymer of vinyl by methyl methacrylate monomer and the optionally monomer mixture preparation of methyl acrylate.Can prepare multipolymer according to letex polymerization, suspension polymerization, solution polymerization or mass polymerization, and it has the weight-average molecular weight of from 20,000 to 250,000 scopes based on vinyl.
According to a kind of further embodiment, be the multipolymer of vinylbenzene and maleic anhydride based on the multipolymer of vinyl, and it can be prepared according to continuous bulk polymerization and solution polymerization.Can in wide scope, regulate the ratio of components of vinylbenzene and maleic anhydride, but in one embodiment,, the amount of maleic anhydride is adjusted to 5 to 50wt% based on the amount of ethylenic copolymer.Vinylbenzene and maleic anhydride copolymers can have the molecular weight of relative broad range.According to a kind of embodiment, it can have the weight-average molecular weight and from 0.3 to the 0.9 ranges of characteristics viscosity of from 20,000 to 200,000 scopes.
Except that alpha-methyl styrene, the styrene monomer that is replaced and can prepare by C1 to C4 alkyl group based on the multipolymer of vinyl can also comprise p-methylstyrene, Vinyl toluene, 2,4-dimethyl styrene etc.
Can be separately or with it two or more mixture uses multipolymer based on vinyl.
Based on 100 weight parts according to (A) of the present invention thermoplastic resin, can add with 0 to 50 weight part based on the multipolymer of vinyl, but in another embodiment, it is in the scope of 0 to 40 weight part.When the multipolymer based on vinyl adds fashionablely in the scope of 0 to 50 weight part, it can provide all consistency, shock-resistance and thermotolerance.
In one embodiment, for (A) thermoplastic resin, can use (A-1) polycarbonate resin and (A-2) mixture based on the graft copolymer of vinyl of modified rubber, and in another embodiment, can use (A-1) polycarbonate resin, (A-2) modified rubber based on the graft copolymer of vinyl and (A-5) based on the mixture of the multipolymer of vinyl.When use (A-1) polycarbonate resin and (A-2) modified rubber based on the graft copolymer of vinyl the time, based on 100 parts by weight of thermoplastic resin, (A-1) polycarbonate resin is with the amount of 45 to 95 weight parts and (A-2) being comprised based on the graft copolymer of the vinyl amount with 1 to 50 weight part of modified rubber.When (A-1) polycarbonate resin and (A-2) modified rubber add fashionablely with the amount of above-mentioned scope based on the graft copolymer of vinyl, it can preferably provide consistency, shock-resistance and thermotolerance.
(B) anionic antistatic agent
Anionic antistatic agent is represented by following Chemical formula 2.
[Chemical formula 2]
C
nH
2n+1——(R
8)
m——R
9 -R
10 +
In above Chemical formula 2,
R
8Be joint (linker), it comprises that replacement or unsubstituted C1 to C5 alkylidene group, replacement or unsubstituted C5 to C6 encircle alkylidene group, replacement or unsubstituted C6 to C10 arylidene or replacement or unsubstituted C2 to C30 heteroarylidene,
R
9 -Comprise sulfonic acid anion, phosphate anion or their combination,
R
10 +Comprise alkali metal cation, alkaline earth metal cation or their combination,
N is the integer of 1 to 35 scope, and
M is the integer of 0 to 3 scope.
In above Chemical formula 2, R
10 +The metallic cation that can comprise sodium, potassium, calcium, lithium, barium, magnesium etc.
Can use anionic antistatic agent separately or as mixture with compound of different n values.When using the mixture of anionic antistatic agent, it can comprise such multipolymer, copolymerization has the anionic antistatic agent that has different n values and have the multipolymer form on this multipolymer, or mixture, the wherein simple anionic antistatic agent that has different n values and have the multipolymer form of mixing.
Based on 100 weight parts according to (A) of the present invention thermoplastic resin, anionic antistatic agent can add with 0.1 to 20 weight part, but in another embodiment, it is in the scope of 0.1 to 10 weight part, and in a kind of further embodiment, it is in the scope of 1 to 5 weight part.Fashionable when adding with 0.1 to 20 weight part based on anionic static inhibitor, can obtain fabulous antistatic property and while excellent heat resistance and mechanical property.
(C) conducting metal oxide
The limiting examples of conducting metal oxide comprises titanium oxide, zinc oxide, Indium sesquioxide, stannic oxide, tin indium oxide (indium tin oxide), weisspiessglanz, zirconium white, aluminum oxide, magnesium oxide, barium oxide, calcium oxide, strontium oxide, chromic oxide, ferric oxide and their mixture.In one embodiment, zinc oxide can be preferred.
In addition, in order to improve the electroconductibility of conducting metal oxide, can use element doping, coating, mixing, mechanical bond or Chemical bond conducting metal oxide such as aluminium, gallium, germanium, indium, tin etc.
In addition, conducting metal oxide can be formed particle, fiber, film, amorphous etc.
Zinc oxide in the conducting metal oxide can be in the group state (group state) of essential structure particle (basicconstituting particle) (primary granule), or secondary curdled appearance, wherein merges and in conjunction with the essential structure particle.According to a kind of embodiment, it has the structure that has wherein produced secondary curdled appearance.
In addition, to have average particulate diameter be the following essential structure particle of 300nm to zinc oxide.According to a kind of embodiment, average particulate diameter is below the 200nm, but in another embodiment, and it is 10 to 100nm.
Based on 100 weight parts according to (A) of the present invention thermoplastic resin, conducting metal oxide adds with 0.1 to 20 weight part, but in another embodiment, it is 0.1 to 10 weight part, and in a kind of further embodiment, it is 0.1 to 5 weight part.When conducting metal oxide adds fashionablely with 0.1 to 20 weight part, it can provide fabulous antistatic property, and it can also provide excellent heat resistance and mechanical property such as shock-resistance simultaneously.
(D) other additive
Antistatic thermoplastic resin composition according to the present invention may further include (if necessary) such as common additives such as antioxidant, fire retardant, lubricant, releasing agent, nucleator (nucleus agent, nuclear agent), thermo-stabilizer, impact modifier, inorganic additives, pigment, dyestuffs.
Antioxidant can comprise phenol, phosphide, thioether or amine antioxidants.
Fire retardant can be bromo, chloro, phosphorated, based on metal hydroxy etc.
Thermo-stabilizer can comprise trimethyl phosphite 99, triphenylphosphate, triethyl phosphate, phosphoric acid or their mixture.
Releasing agent can comprise fluoropolymer, silicone oil, Metallic stearates (stearylicmetal salt), montanic acid metal-salt, montanic acid ester type waxes or polyethylene wax.
Inorganic additives can comprise asbestos, talcum, pottery, vitriol etc.Based on (A) of the present invention thermoplastic resin of 100 weight parts, inorganic additives can add with 0 to 60 weight part, but in another embodiment, it adds with 1 to 40 weight part.
Can be prepared according to the currently known methods that is used to prepare resin combination according to antistatic thermoplastic resin composition of the present invention.For example, it can prepare by following: the constituent according to a kind of antistatic thermoplastic resin composition of embodiment is mixed with other additive, and in extrusion machine it is carried out melt extrusion so that pellet (pellet) to be provided.
Antistatic thermoplastic resin composition can be used for the production of various goods, and it is specially adapted to electric-electronic product shell or is used to make the delivery tray of electric-electronic product.
Hereinafter, explain the present invention with reference to embodiment.Yet these embodiment are illustrative embodiments of the present invention and do not limit the present invention.
[embodiment]
The preparation antistatic thermoplastic resin composition
It is as follows to be used to the constituent for preparing according to thermoplastic resin composition of the present invention.
(A) thermoplastic resin composition's constituent comprises following material.
(1) polycarbonate resin
Bisphenol A polycarbonate with weight-average molecular weight (Mw) of 25,000.
(2) graft copolymer based on vinyl of modified rubber
Add butadiene rubber latex and reach 58 weight parts, add the vinylbenzene of 29 weight parts, the vinyl cyanide of 13 weight parts and the deionized water of 150 weight parts then, so that reactant to be provided up to the amount of divinyl.Add the thiol group chain-transfer agent of the cumene hydroperoxide of potassium oleate additive, 0.4 weight part of 1.0 weight parts and 0.3 weight part and react, simultaneously temperature was remained on 75 ℃, 5 hours, so that ABS (acrylonitrile-butadiene-styrene (ABS)) to be provided graft latex.
Based on the total amount of the graft latex that is obtained, add the sulphuric acid soln of 1wt%, solidify then and dry graft copolymer resin based on vinyl with modified rubber that pulverulence is provided.
(3) polystyrene or rubber modified polystyrene resin
The HG-1760S that use is made by Cheil Industries is as rubber modified polystyrene.
(4) nylon based resin
Make by Zig Sheng (Taiwan), be the nylon 6TP-4210 that has relative viscosity and about 80,000 the number-average molecular weight (Mn) of 2.8cp under 25 ℃ of conditions of using 85% formic acid simultaneously measuring temperature.
(5) based on the multipolymer of vinyl
The vinylbenzene of 72 weight parts, the vinyl cyanide of 28 weight parts and the deionized water of 120 weight parts are mixed, so that reactant to be provided.The Diisopropyl azodicarboxylate of 0.3 weight part, the thiol group chain-transfer agent of 0.2 weight part and the tricalcium phosphate of 0.5 weight part are joined in the reactant, then it is carried out suspension polymerization so that SAN (styrene-acrylonitrile) to be provided copolymer resin.This copolymer resin is washed, dewaters and drying, so that powdered san copolymer resin to be provided.
(B) anionic antistatic agent
Commercial can be available from the trade(brand)name Hostastat that makes by Clariant
(C) conducting metal oxide
Commercial can be available from the conductive zinc oxide (trade(brand)name of making by Japan Hakusui Tech
).
Embodiment 1 to 4
With the amount shown in the following table 1, every kind of constituent is incorporated in the mixing tank so that mixture to be provided.Mixture based on 100 weight parts, the phenol-based anti-oxidants of being obstructed (IRGANOX 1076) of 0.2 weight part and the thermo-stabilizer based on pentaerythritol diphosphites (DOVERPHOS S-9228) of 0.2 weight part are added wherein and mix, extrude to provide pellet to extrude (pelletextrusion) with the twin screw extruder of L/D=35, Φ=45mm then.Under 240 to 280 ℃ injection temperature, pellet is prepared into sample with 10 ounces of syringes.
Comparative example 1 to 5
According to embodiment 1 in identical step prepare sample, difference is, shown in following table 1, to every kind of constituent with and amount regulate.
[EXPERIMENTAL EXAMPLE]
Make in embodiment 1 to 4 and comparative example 1 to 5 sample of preparation be under the condition of 23 ℃ and 50% relative humidity 48 hours, and they are measured with definite physicals according to ASTM (American Society forTesting and Materials) standard.
By the voltage that applies 500V 10cm * 10cm sample is measured, (to make by Mitsubishi Chemical, MCP-HT450) to determine surface resistivity with the URS probe by means of the surface resistivity instrument.
According to ASTM D256 standard, measure 1/8 " the notched izod intensity of sample.
Determine ocular estimate, it depends on crazing (silver streaks) number that produces on 10cm * 10cm injected sample: do not find to be confirmed as " well "; Produce 1 to 3 part and be confirmed as " poor "; And generation is confirmed as " non-constant " more than 3 parts.
The results are shown in the following table 1.
Table 1
As shown in table 1, confirmed to have from 10 according to the sample of embodiments of the invention 1 to 4
6To 10
7The surface resistivity of Ω/ scope.On the other hand, confirmed that the sample that only comprises micro anion type static inhibitor of comparative example 1 does not reduce surface resistivity at all; And the sample that only comprises conducting metal oxide of comparative example 4 does not reduce surface resistivity at all.
Comparative example 2 and 3 the sample that only comprises anionic antistatic agent show aspect surface resistivity and are reduced to 10
10Ω/; Especially, the sample of comparative example 3 makes the shock strength variation significantly.
In addition, even when its used excessive conducting metal oxide, the sample of comparative example 5 also had the similar surface resistivity of sample with embodiment 1 to 4.In addition, it makes the shock strength variation significantly.
Though described the present invention together with being considered to practical illustrative embodiments at present, but should understand, the present invention is not limited to disclosed embodiment, and on the contrary, the present invention is used to contain various improvement included in the spirit and scope of the appended claims and be equal to replacement.
Claims (16)
1. an antistatic thermoplastic resin composition comprises
(A) 100 parts by weight of thermoplastic resin;
(B) anionic antistatic agent of 0.1 to 20 weight part; And
(C) conducting metal oxide of 0.1 to 20 weight part.
2. antistatic thermoplastic resin composition according to claim 1, wherein, described thermoplastic resin comprise the graft copolymer based on vinyl, polystyrene, rubber modified polystyrene resin, nylon based resin of polycarbonate resin, modified rubber, based on the multipolymer of vinyl or their combination.
3. antistatic thermoplastic resin composition according to claim 1, wherein, based on the described thermoplastic resin of 100 weight parts, described thermoplastic resin comprises the graft copolymer based on vinyl of the modified rubber of the polycarbonate resin of 45 to 95 weight parts and 1 to 50 weight part.
4. antistatic thermoplastic resin composition according to claim 1, wherein, described thermoplastic resin is a polycarbonate resin.
5. antistatic thermoplastic resin composition according to claim 1, wherein, based on the described thermoplastic resin of 100 weight parts, described anionic antistatic agent is comprised with the amount of 0.1 to 10 weight part.
6. antistatic thermoplastic resin composition according to claim 1, wherein, based on the described thermoplastic resin of 100 weight parts, described conducting metal oxide is comprised with the amount of 0.1 to 10 weight part.
7. antistatic thermoplastic resin composition according to claim 2, wherein, described polycarbonate resin by making following Chemical formula 1 xenol and compound, halogen manthanoate, carbonic ether or their composite reaction of phosgene obtain:
[Chemical formula 1]
Wherein, in above Chemical formula 1,
A is that singly-bound, replacement or unsubstituted C1 to C5 alkylidene group, replacement or unsubstituted C1 to C5 alkylidene, replacement or unsubstituted C3 to C6 encircle alkylidene group, replacement or unsubstituted C5 to C6 and encircle alkylidene, CO, S or SO
2,
R
1And R
2Be to replace or unsubstituted C1 to C30 alkyl or replacement or unsubstituted C6 to C30 aryl independently of one another, and
n
1And n
2Be the integer of 0 to 4 scope independently of one another.
8. antistatic thermoplastic resin composition according to claim 2, wherein, the graft copolymer based on vinyl of described modified rubber is to obtain by 5 to 95wt% the graft polymerization based on the rubbery polymer of the monomer of vinyl and 5 to 95wt%
Described monomer based on vinyl comprises 50 to 95wt% first monomer based on vinyl, and described first monomer based on vinyl comprises the vinylbenzene of vinylbenzene, α-C1 to C4 alkyl replacement, vinylbenzene, the alkyl methacrylate series that comprises C1 to C8 alkyl, the alkyl acrylate series that comprises C1 to C8 alkyl or their combination that halogen replaces; And 5 to 50wt% second the monomer based on vinyl, described second monomer based on vinyl comprises vinyl cyanide, methacrylonitrile, comprise the alkyl methacrylate series of C1 to C8 alkyl, comprise the alkyl acrylate series, maleic anhydride, C1 to C4 alkyl of C1 to C8 alkyl-or the maleimide that replaces of phenyl N-or their combination, and
Described rubbery polymer comprises divinyl rubber, acryloyl rubber, ethylene/propylene rubber, styrene/butadiene rubbers, acrylonitrile/butadiene rubber, synthetic polyisoprene, ethylene-propylene-diene terpolymer (EPDM), organopolysiloxane/poly-(methyl) alkyl acrylate rubber composite or their combination.
9. antistatic thermoplastic resin composition according to claim 2, wherein, the polymerization of the aromatic vinyl monomer of described polystyrene resin by being selected from the group of being made up of vinylbenzene, p-methylstyrene, alpha-methyl styrene, 4-N-propylstyrene and their combination obtains
The aromatic vinyl monomer of described rubber modified polystyrene resin by being selected from the group of forming by vinylbenzene, p-methylstyrene, alpha-methyl styrene, 4-N-propylstyrene and their combination be selected from by divinyl, isoprene, 1,3-heptadiene, methyl isophthalic acid, 3-pentadiene, 2,3-dimethyl-1,3-divinyl, 2-ethyl-1, the graft polymerization of the rubber of the group that 4-pentadiene and their mixture are formed and obtaining.
10. antistatic thermoplastic resin composition according to claim 2, wherein, described nylon based resin comprises nylon 6, nylon 66, their multipolymer or their combination.
11. antistatic thermoplastic resin composition according to claim 2, wherein, described multipolymer based on vinyl by 50 to 95wt% first based on the monomer of vinyl and 5 to 50wt% second based on the monomeric copolymerization of vinyl and obtain,
Described 50 to 95wt% first monomer based on vinyl comprises the vinylbenzene of vinylbenzene, α-C1 to C4 alkyl replacement, vinylbenzene, the alkyl methacrylate series that comprises C1 to C8 alkyl, the alkyl acrylate series that comprises C1 to C8 alkyl or their combination that halogen replaces;
Described 5 to 50wt% second monomer based on vinyl comprises vinyl cyanide, methacrylonitrile, comprises the alkyl methacrylate series of C1 to C8 alkyl, the alkyl acrylate series that comprises C1 to C8 alkyl, maleic anhydride, C1 to C4 alkyl-or the maleimide that replaces of phenyl N-or their combination.
12. antistatic thermoplastic resin composition according to claim 1, wherein, described anionic antistatic agent is represented by following Chemical formula 2:
[Chemical formula 2]
C
nH
2n+1——(R
8)
m——R
9 -R
10 +
Wherein, in above Chemical formula 2,
R
8Be joint, described joint comprises that replacement or unsubstituted C1 to C5 alkylidene group, replacement or unsubstituted C5 to C6 encircle alkylidene group, replacement or unsubstituted C6 to C10 arylidene or replacement or unsubstituted C2 to C30 heteroarylidene,
R
9 -Comprise sulfonic acid anion, phosphate anion or their combination,
R
10 +Comprise alkali metal cation, alkaline earth metal cation or their combination,
N is the integer of 1 to 35 scope, and
M is the integer of 0 to 3 scope.
13. antistatic thermoplastic resin composition according to claim 1, wherein, described conducting metal oxide comprises titanium oxide, zinc oxide, Indium sesquioxide, stannic oxide, tin indium oxide, weisspiessglanz, zirconium white, aluminum oxide, magnesium oxide, barium oxide, calcium oxide, strontium oxide, chromic oxide, ferric oxide or their mixture.
14. antistatic thermoplastic resin composition according to claim 13, wherein, described conducting metal oxide further comprises the element of aluminium, gallium, germanium, indium, tin or their combination.
15. antistatic thermoplastic resin composition according to claim 1, wherein, described thermoplastic resin composition has less than 10
10The surface resistivity of Ω/.
16. layered product that utilization is made according to the described antistatic thermoplastic resin composition of one of claim 1 to 15.
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| KR20070141913 | 2007-12-31 | ||
| KR10-2007-0141913 | 2007-12-31 | ||
| KR1020080129334A KR101233383B1 (en) | 2007-12-31 | 2008-12-18 | Antistatic thermoplastic resin composition |
| KR10-2008-0129334 | 2008-12-18 |
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|---|---|
| CN101691448A true CN101691448A (en) | 2010-04-07 |
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|---|---|
| KR (1) | KR101233383B1 (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679211A (en) * | 2018-12-26 | 2019-04-26 | 常州胜威塑料有限公司 | A kind of antistatic reinforced polypropylene plastic barrel |
| CN110114403A (en) * | 2016-12-30 | 2019-08-09 | 乐天尖端材料株式会社 | Thermoplastic resin composition and the mechanograph produced by it |
| CN110114405A (en) * | 2016-12-28 | 2019-08-09 | 乐天尖端材料株式会社 | Thermoplastic resin composition and the mechanograph being produced from it |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648411A (en) * | 1995-06-07 | 1997-07-15 | General Electric Company | Thermoplastic blend compositions containing polyester resins and an organosulfate salt |
| US6528572B1 (en) * | 2001-09-14 | 2003-03-04 | General Electric Company | Conductive polymer compositions and methods of manufacture thereof |
-
2008
- 2008-12-18 KR KR1020080129334A patent/KR101233383B1/en active IP Right Grant
- 2008-12-31 CN CN200810190850A patent/CN101691448A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110114405A (en) * | 2016-12-28 | 2019-08-09 | 乐天尖端材料株式会社 | Thermoplastic resin composition and the mechanograph being produced from it |
| CN110114405B (en) * | 2016-12-28 | 2022-06-17 | 乐天尖端材料株式会社 | Thermoplastic resin composition and molded article produced therefrom |
| CN110114403A (en) * | 2016-12-30 | 2019-08-09 | 乐天尖端材料株式会社 | Thermoplastic resin composition and the mechanograph produced by it |
| CN110114403B (en) * | 2016-12-30 | 2021-06-29 | 乐天尖端材料株式会社 | Thermoplastic resin composition and molded article produced therefrom |
| CN109679211A (en) * | 2018-12-26 | 2019-04-26 | 常州胜威塑料有限公司 | A kind of antistatic reinforced polypropylene plastic barrel |
| CN109679211B (en) * | 2018-12-26 | 2021-03-19 | 常州胜威塑料有限公司 | Antistatic reinforced polypropylene plastic packaging barrel |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101233383B1 (en) | 2013-02-15 |
| KR20090073977A (en) | 2009-07-03 |
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