CA2088338A1 - Anti-static agent for thermoplastic polymers - Google Patents
Anti-static agent for thermoplastic polymersInfo
- Publication number
- CA2088338A1 CA2088338A1 CA002088338A CA2088338A CA2088338A1 CA 2088338 A1 CA2088338 A1 CA 2088338A1 CA 002088338 A CA002088338 A CA 002088338A CA 2088338 A CA2088338 A CA 2088338A CA 2088338 A1 CA2088338 A1 CA 2088338A1
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- CA
- Canada
- Prior art keywords
- weight
- nylon
- antistatic agent
- antistatic
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/91—Antistatic compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/91—Antistatic compositions
- Y10S524/912—Contains metal, boron, phosphorus, or silicon
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
- Silicon Polymers (AREA)
Abstract
ANTISTATIC AGENT FOR THERMOPLASTIC POLYMERS
ABSTRACT
An antistatic agent for thermoplastic polymers is provided wherein the antistatic agent is comprised of a functionalized alkylene oxide polymer and optionally a minor amount of an alkali or alkaline earth metal salt capable of complexing with the functionalized alkylene oxide polymer and wherein the thermoplastic polymers include styrenic polymers such as ABS; blends of an ABS copolymer and a styrene-maleic anhydride copolymer; or nylon 6.
ABSTRACT
An antistatic agent for thermoplastic polymers is provided wherein the antistatic agent is comprised of a functionalized alkylene oxide polymer and optionally a minor amount of an alkali or alkaline earth metal salt capable of complexing with the functionalized alkylene oxide polymer and wherein the thermoplastic polymers include styrenic polymers such as ABS; blends of an ABS copolymer and a styrene-maleic anhydride copolymer; or nylon 6.
Description
2~3~
ANTISTATIC AGENT FOR THERMOPLASTIC POLYMERS
BACKGROUND OF THE INVENTION
The present in~ention relates generally to an antistatic agent for thermopla~tic polymers and to thermoplastic compositions containing such an agent.
Many thermoplaskic compositions, including ABS compositions, exhibit relatively slow electrostatic charge dissipation rates which make them unacceptable for many applications, i.e., housing for optical and magnetic recording media, medical davices and military equipment.
one method used to raise the electrostatic charge dissipation rates of these compositions is to incorporate a hydrophilic, moderately incompatible material with antistatic properties into the composition.
Types of these so-called i'internall' antistatic materials or agents include ethoxylated amine chemicals and homopolymers and copolymers o~
~thylene oxide, such as polyethylene oxide and epichlorohydrin rubber.
These antistatic agents function by continually migrating to the surface o~ the composition, because of their limited compatibility, to form a continuous film on the æur~ace. Moisture is attracted to the surface of the composition by these antistatic agents thereby decreasing the static charge.
Unfortunately, the antistatic agents currently known have certain disadvantages.
Included among these disadvantages are degradation o~ the compositions physical and mechanical properties due to the presence of the antistatic agent; inadequate electrostatic charge dissipation rates; functional dependence on the amount v~
ANTISTATIC AGENT FOR THERMOPLASTIC POLYMERS
BACKGROUND OF THE INVENTION
The present in~ention relates generally to an antistatic agent for thermopla~tic polymers and to thermoplastic compositions containing such an agent.
Many thermoplaskic compositions, including ABS compositions, exhibit relatively slow electrostatic charge dissipation rates which make them unacceptable for many applications, i.e., housing for optical and magnetic recording media, medical davices and military equipment.
one method used to raise the electrostatic charge dissipation rates of these compositions is to incorporate a hydrophilic, moderately incompatible material with antistatic properties into the composition.
Types of these so-called i'internall' antistatic materials or agents include ethoxylated amine chemicals and homopolymers and copolymers o~
~thylene oxide, such as polyethylene oxide and epichlorohydrin rubber.
These antistatic agents function by continually migrating to the surface o~ the composition, because of their limited compatibility, to form a continuous film on the æur~ace. Moisture is attracted to the surface of the composition by these antistatic agents thereby decreasing the static charge.
Unfortunately, the antistatic agents currently known have certain disadvantages.
Included among these disadvantages are degradation o~ the compositions physical and mechanical properties due to the presence of the antistatic agent; inadequate electrostatic charge dissipation rates; functional dependence on the amount v~
3 ~
-2- 0~-12~8889 moisture in the surrounding atmosphere; and reduction over time of the antistatic agents ability to decay surface charge as a result of wiping, rinsing, aging or blooming of the agent.
It is therefore a primary object of the present invention to provide an antistatic agent that is durable; serves to maintain or enhance the host compositions' mechanical prop~rties; and which produces a highly conductive antistatic thermoplastic composition irrespective of the amount o~ moisture in the surrounding atmosphere.
It is a further object of the present invention to provide an antistatic thermoplastic composition that incorporates the inventive antistatic agent.
SUMMARY OF T~IE INVENTION
The present invention is directed to an antistatic agent for thermoplastic polymers and ts thermoplastic compositions containing such an agent. The antistatic agent comprises a functionalized alkylene oxide polymer selected from the group consisting o~ polyethylene oxide, polypropylene oxide, polybutyl~ne oxide, copolymers of ethylene oxide and propylene oxide, and polydimethylsiloxane carbinol terminated poly(ethylene oxide-dimethylsiloxane-ethylene oxide) ABA block copolymers and blends thereof where the functional group of the functionalized alkylene oxide polymer is selected from the group consisting of hydroxy, epoxy and amino groups; and optionally a minor amount of an alkali or al~aline earth metal salt.
It has been ~ound that thermoplastic compositions containing the inventive antistatic agent demonstrate an acceptable balance oE
~Q~3~3~
mechanlcal propertie~ and a high level o~ ntatic charge decay.
.
DETAILED DESCRIPTION OF THE INVENTION
The antistatic agent o~ the present invention is comprised of a functionalizsd alkylene oxide polymer and optionally a minor amount o~ an alkali or alkaline earth metal salt capable of complexing with the functionalized alkylene oxide polymer.
Preferably, the antistatic agent comprises a functionalized alkyl~ne oxide polymer and a minor amount of an alkali or alkaline earth metal salt. More preferably, the antistatic agent is comprised of from 99.9 to 90% by waight of the polymer and from 0.1 to 10% by weight of the metal salt.
The alkylene oxide polymers that are contemplated by the present invention include polyethylene oxide, polypropylene oxide, polybutylene oxide, copolymers o ethylene oxid~
and propylene oxide, and polydimethylsiloxane carbinol terminated poly(ethylene oxide-dimethylsiloxane-ethylene oxide~ ABA block copolym~rs and blends thereof, the preferred alkylene oxide polymer being polyethylene oxide~
The functional groups for thP alkylene oxide polymer include hydroxy, epoxy and amino groups, with hydroxy and amino groups being pre~erred. The preferred functionalized polymer is amine functionalized polyethylene oxide.
Alkali and alkaline earth metal salts used in the present invention are those metal salks that are capable of complexing with the functionalized alkylene oxide polymer. Preferr~d are those metal salts with small cations and large 3 ~ 3 ~
-~- 08-12-8889 anions~ such as lithium chloride, lithium acetate, lithium carbonate, lithium tri~luoromethyl sulphonate and sodium acetata.
The preferred antistatic agent is comprised of from 99.9 to 90% by weight of amine functionalized polyethylene oxide and from o.l to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate.
The alkali or alkaline earth metal salt is added to the functionalized alkylene oxide polymer by pre~erably first forming an aqueous solution of the metal salt and then adding this solution to the warm liquid pol~mer.
. The thermoplastic composition of the present invention comprises a thermoplas~ic polymeric component and the antistatic agent set forth above.
The thermoplas~ic polymeric components include, but are not limited to, styrenic polymers, polyamides, polycarbonates, polyolefins, polyureas, polyurethanes and blends thereof. Styrenic polymers include polystyrene, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene-acrylate copolymers, methacrylate-butadiene-styrene copolymers, styrene-maleic anhydride copolymers, styrene-methyl methacrylate copolymers, styrene-maleic anhydride-methyl methacrylate copolymers and blends thereof. The polyamides include homopolymers and copolymers of polyamides and mixtures thereof. Examples of the polyamide resins are homopolymers such as nylon 6, nylon 66l ~ylon 4, nylon 8, nylon 11, nylon 12, nylon 69, nylon 610, and nylon 612; and copolymers such as nylon 6/66, nylon 6/12, nylon 6l69, and lactam-lactone copolymers. Pre~erably, the polymeric component is 2a~33~
-2- 0~-12~8889 moisture in the surrounding atmosphere; and reduction over time of the antistatic agents ability to decay surface charge as a result of wiping, rinsing, aging or blooming of the agent.
It is therefore a primary object of the present invention to provide an antistatic agent that is durable; serves to maintain or enhance the host compositions' mechanical prop~rties; and which produces a highly conductive antistatic thermoplastic composition irrespective of the amount o~ moisture in the surrounding atmosphere.
It is a further object of the present invention to provide an antistatic thermoplastic composition that incorporates the inventive antistatic agent.
SUMMARY OF T~IE INVENTION
The present invention is directed to an antistatic agent for thermoplastic polymers and ts thermoplastic compositions containing such an agent. The antistatic agent comprises a functionalized alkylene oxide polymer selected from the group consisting o~ polyethylene oxide, polypropylene oxide, polybutyl~ne oxide, copolymers of ethylene oxide and propylene oxide, and polydimethylsiloxane carbinol terminated poly(ethylene oxide-dimethylsiloxane-ethylene oxide) ABA block copolymers and blends thereof where the functional group of the functionalized alkylene oxide polymer is selected from the group consisting of hydroxy, epoxy and amino groups; and optionally a minor amount of an alkali or al~aline earth metal salt.
It has been ~ound that thermoplastic compositions containing the inventive antistatic agent demonstrate an acceptable balance oE
~Q~3~3~
mechanlcal propertie~ and a high level o~ ntatic charge decay.
.
DETAILED DESCRIPTION OF THE INVENTION
The antistatic agent o~ the present invention is comprised of a functionalizsd alkylene oxide polymer and optionally a minor amount o~ an alkali or alkaline earth metal salt capable of complexing with the functionalized alkylene oxide polymer.
Preferably, the antistatic agent comprises a functionalized alkyl~ne oxide polymer and a minor amount of an alkali or alkaline earth metal salt. More preferably, the antistatic agent is comprised of from 99.9 to 90% by waight of the polymer and from 0.1 to 10% by weight of the metal salt.
The alkylene oxide polymers that are contemplated by the present invention include polyethylene oxide, polypropylene oxide, polybutylene oxide, copolymers o ethylene oxid~
and propylene oxide, and polydimethylsiloxane carbinol terminated poly(ethylene oxide-dimethylsiloxane-ethylene oxide~ ABA block copolym~rs and blends thereof, the preferred alkylene oxide polymer being polyethylene oxide~
The functional groups for thP alkylene oxide polymer include hydroxy, epoxy and amino groups, with hydroxy and amino groups being pre~erred. The preferred functionalized polymer is amine functionalized polyethylene oxide.
Alkali and alkaline earth metal salts used in the present invention are those metal salks that are capable of complexing with the functionalized alkylene oxide polymer. Preferr~d are those metal salts with small cations and large 3 ~ 3 ~
-~- 08-12-8889 anions~ such as lithium chloride, lithium acetate, lithium carbonate, lithium tri~luoromethyl sulphonate and sodium acetata.
The preferred antistatic agent is comprised of from 99.9 to 90% by weight of amine functionalized polyethylene oxide and from o.l to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate.
The alkali or alkaline earth metal salt is added to the functionalized alkylene oxide polymer by pre~erably first forming an aqueous solution of the metal salt and then adding this solution to the warm liquid pol~mer.
. The thermoplastic composition of the present invention comprises a thermoplas~ic polymeric component and the antistatic agent set forth above.
The thermoplas~ic polymeric components include, but are not limited to, styrenic polymers, polyamides, polycarbonates, polyolefins, polyureas, polyurethanes and blends thereof. Styrenic polymers include polystyrene, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene-acrylate copolymers, methacrylate-butadiene-styrene copolymers, styrene-maleic anhydride copolymers, styrene-methyl methacrylate copolymers, styrene-maleic anhydride-methyl methacrylate copolymers and blends thereof. The polyamides include homopolymers and copolymers of polyamides and mixtures thereof. Examples of the polyamide resins are homopolymers such as nylon 6, nylon 66l ~ylon 4, nylon 8, nylon 11, nylon 12, nylon 69, nylon 610, and nylon 612; and copolymers such as nylon 6/66, nylon 6/12, nylon 6l69, and lactam-lactone copolymers. Pre~erably, the polymeric component is 2a~33~
-5- 08-12-8~89 acxylonitrile-butadiene-styrene copolymer; a blend of from 98 to 80% by weight acrylonitrile-butadiene-styrene copolymer and from 2 to 20~ by weight skyrene-maleic anhydride copolymer, nylon 6;
nylon 66; or nylon 6/56 copolymer.
It has been observed th~t when a polyamide polymeric component is used, addition o~
an alkali or alkaline eaxth mstal salt alone will result in a composition displaying comparable antistatic properties to those realized by compositions employing the antistatic agent set forth above.
The antistatic agent may be incorporated into the thermoplastic polymeric component of the inventive antistatic thermoplastic composition by conventional melt blending techniques, such as reactive extrusion or mixing in a Banbury mixer where residual water is flashed off followed by a drying step just prior to feeding to a pelleti~ing device.
The antistatic agent may also be incorpor~ted into the thermoplastic polymeric component by copolymerizing the antistatic agent with copolymerizable monomers of the polymeric component. ~his is especially useful with polyamides.
In a preferred embodiment, the antistatic thermoplastic composition of the present invention is comprised of (1) from 95 to 80% by weight of acrylonitrile-butadiene styrene copolymer; and (2) from 5 to 20% by wei~ht of an antistatic agent comprising a3 from 99.9 to 90% by weight o~'amine ~unctionalized polyethylene oxide; and b) ~rom 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate.
3 ,~ 3 ~ ~
-~ o~-12-8889 In a more prefarred embodiment, the antistatic thermoplastic composition is comprised of (1) from 95 to 80% by weight of a styrenic polymer blend comprising a) from 98 to 80% by weight of acrylonitrile-butadiene-styrene copolymer; and b) ~rom 2 to 20% by weight of styrene-maleic anhydride copolymer, and 52~ from 5 to 20~ by weight of an antistatic agent comprising a) from 99.9 to 90% by weight of amine functionalized polyethylene oxide; and b) :Erom 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate. In the more preferred embodiment, ~t is further preferred that the mole ratio of free amine to anhydride in the inventive composition be about 1:5. It is believed that the reactive anhydride groups in the styre~e-maleic anhydride copolymer anchor the polyethylene oxide through the amine groups.
In another more pre~erred embodiment, the antistatic thermoplastic composition is co~prised of (1) from 95 to 80% by weight of nylon; and (2) from 5 to 20% by weight of an antistatic agent comprising (a) from 99.9% to 90% by weight of amine functionalized polyethylene oxide; and (b) from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate.
Other known additiYe~, such as impact modifiers, pigments, lubricants, stabilizsrs, fillers, antioxidants and flow aids may also be included in the antistatic thermoplastic compositions of the present invention provided such additives do not adversely affect the static'charge decay abilities of the resulting compositionO
In addition to th~ above description, the antistatic agent and antistatic thermoplastic composition of ths present invention are further ~ 3~3~
-7- 08~12-8~89 developed by reference to the illustrative, but not limiting, examples set forth below.
WO~ING EX~MP~ES
In the Working Examples s2t ~orth below, 5 the following components were used:
ABS - a rubber graft copolymer o~
butadiene and styrene (90/10% by weight) grafted with styrene and acrylonitrile wherein 65% by weight is styrene and 35% by weight i~
acrylonitrile. This intermecliate ABS was further diluted with styrene acrylonitrile copolymer as set forth below.
SAN - a copol~mer of 68% by weight based on the weight of the copolymer of styrene and 32% by weight o~
acrylonitrile.
SMAMMA - a copolymer of 68% by weight based on the weight of the copolymer of styrene; 25~ by weight of maleic anhydride; and 7% by weight of methylmethacrylate.
N6 - nylon 6 prepared as set ~orth herein.
PED ~mol. wt.] ~ polyether diaminas ~hich are predominantly polyethylene oxide with some polypropylene oxide sold by Texaco Chemical Company under the name Jeffamine~ ED series.
Bra~keted number denotes mole~ular weight.
PPP [mol. wt. range: E0% range] -polydimethylsiloxane carbinol terminated poly(ethylene oxide-2 ~
-8- 08~ 9 dimethylsiloxane-ethylen~ oxide~ ABA
block copolymer available from Huls America. Bracket~d numbers denote molecular weight range; ethylene oxide percentage range.
PE0 [mol. wt.J - polyethylene oxide available fro~ Union Carbide Company.
Bracketed number denotes molecular weight.
PED0 - polyether diol available from Union Carbide Company.
PEG [mol. wt.~ - polyethylene glycol available from Union Carbide Company.
Bracketed number denotes molecular weight.
PSSS - poly(styrene-4-sulphona~e) sodium salt svld by Scientific Polymer Products Company.
PAAS - poly(acrylic acid) sodium salt sold by Scientific Polymer Products Company.
MGS - magnesium stearate available ~rom C.P. Hall Co.
A-410 - ethoxylated alkyl amine sold by AXzo Chemie ~merica under the name Armostat 410.
A-C - a bis-ethylene diamine stearamide sold by Lonza Inc. under the name Acrawax C.
S~160 - n-butylbenzyl phthalate sold by Monsanto Chemical Company under the name Santicizer-160.
I-1076 - a hindered phenol type antioxidant sold by Ciba-Geigy Corp. under the name of Irganox 10'76.
, 3 3 ~
~-9~ 12-8889 CATALYST - a mayn~sium bromide caprolactam adduct with a melting point of abou~
70~C having a concen~ration of 1~0 mol~ of maynesium bromide per kilogram of caprolactam (21.6 wt. %
adduct; 78.4 wt. % caprolactam) - obtained from Grant Chemical Division of Ferro Corporation of Baton Rouge, Louisiana.
INITIATOR - iscphthaloyl biscaprolactam prepared by adding one (1) mole of bisacyldichloride to two (2~ mol~s of caprolactam. The ~ICl formed was neutralized with an amine and the product recovered.
The following laboratory r~agent grade chemicals were obtained from Aldrich Chemical Company and used without fur~her purification:
Lithium Chloride (LiCl) Lithium Acetate (LioAc) Lithium Carbonate (Li2Co3) Lithium Trifluoromethyl Sulphonate (LiCF3So3) Sodium Acetate (NaOAc) SAMPLE PREPARATIQN
The Working Examples set forth below, with the exception of the antistatic polyamide compositions, were prepared by compounding using a 3.4 kg. Banbury mixer. All solid intermediates including polymeric components and additives'such as antioxidants and flow aids were weighed and dry blended before adding to the Banbury mixer once the correct operating temperaturPs were reached.
(}
-10 08~ B889 Low molecular weight PEO additive~, having a molecular weight of less than or equal to 6000, which were generally waxy solids at room temperature, were pre-weigh~d inko glass jars and melted in a microwave oven just before addiny to the Banbury mixer.
Examples containing PED coordinated with alkali or alkaline earth metal salts were prepared by first dis601ving the salt as a 10 to 20%
solution in water and gradually adding this solution to mechanically stirred liquid PED, melted at 50 to 60C. The resulting aqueous PED/alkali or alkaline earth metal salt was then added to the dry blend in the Banbury mixer.
Working Examples containing polymeric sodium salts, poly(acrylic acid) and poly(styrene-4-sulfonate), were prepared by mixing these additives in with the dry blend in the Banbury mixer.
High gloss workiny examples which used high molecular weigh~ PEO (MW>6000) coordinated with an alkali or alkaline earth metal salt were prepared by mixing the PEO with the dry blend and adding an aqueous solution of 10 to 20% by weight alkali or alkaline earth metal salt directly to the Banbury mixer.
Set conditions for the Banbury mixer were ~s follows:
Circulating Oil Temperature 107C
Rotor Speed 100 rpm Ram Weight Air Pressur~ 0.41-0.55 MPa Post Flux Dump Time 60-80 ~ec.
Dump Temperature 215C
The compounded blends were dried thoroughly in a hot air ~irculating oven at 75 to 3~
~ 08-~2-8~89 80C for 24 hours or in a vacuum oven with a nitroyen bleed for 18 hours at the same temper-ature, prior to injection molding te~t specimens.
Molding was carried out on a 4 oz.
5 Arburg molding machine under the following general conditions-Zone 1 Temp., C 225 225 Zone 2 225 225 Zone 3 230 230 Nozzle Temp., C 230 230 Screw Speed, rpm 200 200 Injection Pressure, MPa 7.41 7.65 Mold Temp., C 120 120 .
The freshly molded specimens w~re conditioned for at least 24 hour~ at 23~C at 50%
relative humidity unless otherwise stated.
Examples 33 to 39 below illustrate the incorporation of the antistatic agent into a polyamide by copolymerization of a polyamide ~orming monomer with the metal salt complexes used as antistatic agents in th~ present invention. In Examples 33 to 38, caprolactam is used as the polyamide forming monomer while in Example 39, a combination o~ caprolactam and caprolactone is used to form a nylon copolymer having the antistatic agent as part of the copolymer backbone. When caprolactone is present it complexes with the metal salt, e.g. LiCl. The examples were prepared a~
~ollows: the metal salt was dissolved in water and an antistatic agent component ~i.e., PEO, PED;
PEDO; or PEG) was weighed out into a heated glass jar and then agitated on a magnetic stirring hot plate. During agitation, the metal salt/water solution was added and the resulting mixture 2~3~
-12- 08-12-88~9 agitated on the ma~netic stirring hot plate for 2 to 5 minutes. The mixture was then dried overnight in a vacuum oven at 90C under full vacuum. Hot molten caprolactam (<lOOppm moisture; mp = about 69C~ or caprolactone (distilled prior to u~e) was added to the dried mixture and the mixture maintained at between 110 and 130C until the caprolaotam or caprolactone wa~ dissolved. ~pon dissolution, thP initiator was added to form Reactant A.
In a second glass jar, caprolactam was weighed out and the catalyst dissolved therein to form Reactant B.
Reactant A and Reactant B were th~n mixed together and the resulting mixture poured into a 160~ stationary mold and allowed to polymPrize.
Polymerization times ranged from 5 to 7 minutes.
Test bars were routed from the resulting plaques and conditioned for at least 24 hours at 23C at 50~ relative humidity prior to testing.
TEST METHODS
The molded specimens and test bars were then subjected to the following tests:
Tensile properties - ASTM D636;
Flexural properties ~STM D790;
(Tensile and Flexural properties were measured o~
an Instron tester using 0.32 cm. tensile bars or 12.7 cm. x 1.27 cm. x 0.32 cm. bars.) Notched Izod Impact - ASTM D256;
HDTUL - ASTM D648 at 0.46 MPa fiber ~tress;
Vicat softening point - A5TM D1525 unde~ 1 Kg load;
Multiaxial Inverted ~art Impact ~IDI~ - The IDI determination utilized represents a modification of the test as described in 2~3 ~3~
-13 ~ ~ 12-88~9 Society of Plastics Engineers National Technical Conference l'Plastics in Surface Transportationl' Nov. 12-14, 1974, Detroit, Michigan, at page 238. In the modified test, instead o~ the dart being attached to the slider and striking the sample, the sample holder iæ aktached to the slider and strikes the instrumented dart. The rotary potentiometer is not used. The instrumented dart used is 1.2 cm. in diameter, and the sample strikes the instrumented dart at a velocity of 140.2 m/minO The samples were injection molded into 7.62 cm. x 10.2 cm. x 0.32 cm. plaques and then cut into two 5.08 cm. x 7.62 cm. piecss for testing.
Results are given in Joules (J).
Surface Gloss - measured using a Gloss Guard 11 device at an angle of 60;
% Charge Decay - a l'Static Honest Meter" was used to measure dissipation of electrostatic charge according to khe saturakion charged voltage. An electric charge was accumulated on the surface of the sample, until it reached a saturation voltage of 700v, by means o~ corona discharge. The discharge was then stopped and a sensing electrode used to record the surface electric charge decay with time in seconds. The % charge decay was then calculated from the data obtained at the specified time.
~ .3~7 -l4- OB-l2-8889 EXAMP1E5 Cl AND 1 TO 5 In thes0 Examples, molded specimens containiny PED and/or PPP and SMAMMA were tested for mechanical strength and static decay properties. The results ~re tabulated in Table I.
3 ~ 3 l~
SUM~ARY 0~ EX~MPLES C-l_A~ 1 qD 5 E~MP1~ C-1* 1 2 3 4 5 oo~PQNENTS (% by weight) SAN 6~ 50 50 50 50 ~0 SM~MM~ _ - 15 15 15 _ 15 ~15 _ (E~) PED [6000] - 5 10 - - 5 PPP [2200-2600, - - - 5 10 5 45-55%J
A-C 0.8 0.8 0.8 0~8 0.80.8 I-1076 _0.2 0.2 0.2 0.2 0020.2 PRf)~ES
Tensile Str (MPa)44.4 37 32.1 34.128.9 26.7 Iensile ~d (Gæa) 2.7 2.3 2.4 2.52.3 2.1 ElQngation (%)6 42 83 23 6 5 IDI Emax (J)4.7 9.2 23.1 6.6 5.4 11 Efail (J~5.2 3.5 37.6 7.2 6.212.8 Izod Impact 211.89.6 26.8 7.5 6.711.7 Notched (KJ/m ) (MB) (NB) ~DqUL ( C) 84 89 87 86 81 8~
~ica~, IK3 ( C) 103 112 111 108104 107 % Charge Decay at T = lOs.10 4 50 31 34 4 * C 1 oontains 1~ by weight o~ ~-410.
NB = Not broken.
2 ~ 3~' -16- 0~12 ~8 Examples 1 to 5 demonstra~e ~he ef~ect o~
adding PED and/or PPP to an ABS/S~MMA blend.
Example 1 which incorporated PED and SMAMMA, although able to e~fect static decay, showe~ no static decay improvement over the Control C~1 which utilized the priox art antistatic agent, A-410, in the absence of SMAMNA. Example 2, in which the amount of PED was increased from 5 pph to 10 pph, as compared to Example 1, showed a substantial improvement in its ability to achieve fast static charge decay in addition to showing a substantial improvement in both IDI and notched Izod ~no break in 7.62 cm. bars) impact properties.
There was little change in the tensile modulus and heat (HDTUL at 87C) ~f Example 2 as compared to Example l. Examples 3 and 4, which utilized 5 pph and 10 pph PPP respectively, demonstrated a similar ability to achieve fast static charge decay, as compared to Examples 1 and 2, although the resultank resin showed slightly lower impact properties.
Example 5 which incorporated 5 pph each of PED and PPP along with SMAMMA also demonstrated an ability to achieve static charge decay and demonstrated improved impact properties as compared to Examples 3 and 4.
In Examples C-2 and 6 to 1~, molded specimens containing varying amounts of SAN, SM~MMA
and PED were tested. The re~ults are set forth in Table II. I
~ ~ g ~
I!~E II
St~RY OF EX1~ C-2 AND ~ TO 10 EXP.M~C--2 6 7 8 9 1 ~ = (~ by wei~jht) A~S 35 35 35 35 35 35 SPN 5~ 55 60 ~5 55 55 VE~ (PE h) P~D t6000] - 10 8 10 15 20 10 A-C 0.8 0.8 0.8 0~8 0.8 0.8 I-1076 0.2 0.2 0.2 0.2 0.2 0.2 % M~ noles/100 g) 26 26 13 %-NH2 (~ ~les) 0 3.3 2.6 Ratio M~/-NH~ _- 7.9 4.9 15 PRf)PEgIl~S
Tensile St~ (MPa) 49.329~6 30.5 29.9 27.2 21.8 Tensile M~d (OE'a) 2.8 2.4 2.5 2.1 2.1 1.7 El~gation (%) 7 97 112 92 55 78 IDI Emax (J) 1.3 14.520.6 16.7 18.5 11.6 20 Eeail (J) 1.4 20.933.5 252g.4 14.a~
Izod ~act 2 3 26 26 28.1 25.8 22.7 Nc~tched (XJ/m ) HD~ (C) 91 85 8~ 83 82 ND
Vicat, 1~ (C) 112 109 108107 106 ND
25 % C~an3e Decay at T = lOOs. 0~28 26 27 61 48 90 ND = Not De~mi~.
~a~33~
-18- OB-12~8889 Examples 6 and 7 demonstrate the effect of varying the amounts of SAN, SMAMMA and PED in the blend. In particular, these Examples show the best combination of these components or the best mole ratio o~ free amine to anhydride in the blend in terms of achieving optim~m mechanical properties.
From the r~sults set forth in TabIe II, it appears that the best combination of impact, heat and modulus is obtained in Example 7 with 5%
SMAMMA and 8pph PED with a mole ratio of free amine to anhydride in the blend of approximately 1-5.
Examples 8 to 10 show the effect of increased amounts of PED on the mechanical properties of the blend. From the results set forth in Table II, it appears that although increased amounts of PED in the ABS/SMAMMA blend typically improve the blends static charge decay ability amounts in excess of 15 pph adversely affect the blends mechanical properties.
In these Examples, th~ effect of lithium chloride addition on the molded specimens' mechanical strenqth and static decay properties were measured. The results are tabulated in Table IIIo In Examples 15 to 21, the amounts of each additive are expressed as parts per hundred parts of the polymeric component.
2~3~
-19-- 08- 12 -88~9 rJ ~
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o o ~ ~ i o ,~ c lY ~ ~ 1 ~1 ,~ ~ ~ o~ ~
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~r ~ I~ OD
O 1` 0 ~J O
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~ ~ u~ o m o r~ o ~ o u~
1~ ~ u~ ~
~ ~ ~ a~1 ~ O O ~ CO a~ ~1 Hl t~ ~n~1 0 HC~ lf) CO ~
~ ~ ~ ~ o o ~ ~ ~ 1 o ô d' C~
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u~ m r o ~ a ~ ~y ~1 ~ u~ o o s: r~ ~ o o~
~Ul ;~
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2~ ~33~
Examples 11 to 15, prepared by incorporating LiCl, suspended in PED, in with the ABS/SMAM~A blend in a Banbury mixer, demonstrate the e~fect of LiCl addition on the resulting blendsl static charge decay ability~
Examples C 3 and 11, as set forth in Table III, show that the addition of LiCl suspended in PED to the ABS/S~AMMA blend results in an improvement in static charge decay ability.
lQ Examples C3 to 14 demonstrate that as the % LiCl level increased from 0 to 1.5%, khe static charge decay ability also increased~ Examples 13 and 15 show that increasing the amount of PED favorably affects the static charge decay ability and does not affect the matPrials impact properties. It was observed that materials molded from the blends with higher salt contents showed phase separated crystals of LiCl on the surface. This may account for the improved ~tatic charge decay and the lower observed impact strengths of these materials.
Examples 16 to 20 show the effect of using the preferred preparation method initially set ~orth and varying the amounts o~ polymeric component levels on the resulting materials impact strength.
Examples 16 to 20 demonstrate, in general, that preparation of these blends according to the preferred preparation method, in comparison to the method outlined for Examples 11 to 15 above, favorably effects the r~sulting materials Xzod strength. Examples 16 to 18 show that decreasing the ABS level understandably results in slig~tly decreased Izod strengths. Example 19, in comparison to Example 17, and Example 20, in comparison to Example 18, demonstrate that s~
~ 0~ 8889 increased levels of P~D and ~iCl also result in ~lightly decreased Izod ~tr~ngths.
~ xample 21 represents an optimized blend that demonstrates good mechanical properties and notable % Charge Decay at T = lOs. Example 21 incorporates S-160 instead of A-C plasticizer.
In Examples C-4 and 22 to 24, certain polymeric salt~ were evaluated in place of LiCl according to the formulations set forth below in Table IV.
~,3~C3~
~I r~ ~! 'P tn ~ 111 O 11~ 1~ 1 Itl ~ t~l O ~ 11~ 1~ r~
t`i 1 ~D rl N N
d ~
~ ~ Itl O In ~ d' ~
) t~ 1~1 O 1~1 In N I d' t~ ~ d' t~ rl rl t~ ~ ~o r~ ~ ~t 00 ~ ~D
rl u~ o In In I I ~ ~ ~
_ r-l ~r~ Ul rl N r1 OD rl ~ ~ ~ ~p ~ ~ , _ h ~
In o 2 0 ~ 3 ~ 3 ~3- oa-l2-~889 Examplas 22 to 24, in comparison to Control C-4, demonstrate that both polymeric salts utilized are success~ul in effecting rapid charge decay. Although the impact properties o~ these materials was decreased, these properties are still within acceptahle limits for some applications.
~IPL~S C--5 A~ 2 5 '10 2 8 In Examples C-5 and 25 to 28, several alternative salts were evaluated in place of hiCl.
The results are tabulated în Table V~
~ ~ ~ O ~3~ c'~ () --2~-- 08--~2~888~
~ In ~
co u~ o u~ ~ ~! o ~r ~ ~ G~ r~ ~ ~ a~ ~ ~ t~
~ 1` ~D rl ~ N ~ ~ ~I N~ t~ ~
~) I
~` 1~ 0 l~ ~ 1~ r-i cn o X '~
g ~ ~ o~
1~ U) ~ ~1~ ¦ ~ cn ~') ~i NN 1` ~ 1`
P ~
In ~ o ~ ~ ~ o ~P ~i o ~ ;i o ~D ~ ~ tl1 0 ~ ~ O~
~n ~3 ~ O c~
__ ~ _ O U~.
20($(~33~, -25- ~8-12 888~
Examples 25 to 28 demonstrate the ability of salts other than LiCl to ef ~ect comparable static decay while maintaining or improving the resultant blends~ mechanical properties. Most notable is Example 27, which incorporates likhium trifluoromethyl ~ulphonate ~triflat~) salt, and which demonstrates comparable % Charge Decay as in Control C-5 utilizing LiCl, but which results in a blend with improved impact strength.
EXAMPLES C-6 ~ND 29 TO 32 In Examples C-6 and 29 to 32, high molecular weight PED's complexed with LiCl were used in melt blends with ABS/SMAMMA to achieve antistatic materials with high surface gloss~ The results are tabulated in Tabl~ VI.
2f~(3~3 -33~
-26- 08-12-~89 ~I U) 11) 0 1~ o N O N ~ ~D ~ D
u~ ~
~1 u~ o u~ r~ o r~ D 0 ~D In r~ I r1 QO 0~ 03 ~ In O In O It~ ~ O ~ t`' N L~ r` O ~r 1~ 1` ~1 al r~ t~7~O ~1 l U~
~ C~ 0~ 1~ 0 U~ ~ O O ~ N 1~ ~r ~ W OD 11~ ~r ~ OD
~ ~ç3 1~ ~ D ~_1 ~ !~
~ ~ lO O u1 ~ o tO r- N ~) N ~ CO N 11~ ~
_ , ,~
.~ _ ~
,~
o ~1 ~1o~ ~ 3 ~ ~ ~1 ~ @ ~ ~1 o o In o u~
~ ,, 2 Q (~ ~ t) rl (~
-27- ~8~ 8B89 5ignificant % Charge Decay at T a 5 seconds was demonstrated in Control C-6 and in Example~ 29 to 32.
Control C 6 which utilized a P~D having a molecular weight of 6000 produced a material having inherently low surface gloss. In comparison, Examples 29 and 31 which utilized PEDIs having molecular weights o~ 12,000 and 100,000 respectively demonstrated increased surface gloss lo while Example 30 which utilized a 50/50 mix of 300/600K PED achie~ed a ~ery high gloss of 94%. In addition, the mechanical strength (flex and tensile), the IDI and notched Izod impact strengths and the thermal properties of Example 30 were improved over Control C-6. Examples 31 and 32 show that the absence of SMAMMA in the inventive "high gloss" composition increases the % gloss, but lowers the % Elongation and IDI strength.
In Examples 33 to 38, test bars of antistatic nylon 6 homopolymer compositions containing PED, PEG, PE0, or PED0 and lithium chloride were tested for static charge decay abilities. In Example 39, a test bar of a nylon 6 copolymer containing about 11.7% by weight of caprolactone composition that employed lithium chloride was also tested for static charge decay abilities.
3 3 ~
~8~ 0~ 12-8~89 T~E~VII
S~RX OF EX~E~ 33 TO 39 E~ E 33 34 35 36 37 38 39_ coM~In~ns (% by weight) N6 100 100_ 1OO 100 100 lOQ 8 ~ 7 PED [6000] ~ 13.2 PEG [lO,OGO] - 13.2 ~ 26.3 PE~ ~300,000] 6.1 ~
PE~ [lQO,OOO] - - - - 6.1 PEDO - - 13.2 - - - -LiCl 1.4 1.4 1.4 1.4 1.4 1.4 1.4 I~n~OR 2.1 2.1 2.1 2.1 2.1 2.1 2.1 CAr~YST 15.8 15.~ ~5.8 15.8 15.8 15.8 15 8 PRQP ~lES
% o~e Decay a~ T = ~Os. 83.1 100 89.1 100 100 100 100 * Contains 88.3% by weight caprolactam and 11.7% by weight caprolactone.
2 f~
~29- 08-12-8~B9 In high glo65 Examples 33 and 37, which used high molecular weight PEO (MW = 300,000 and MW
= lOO,oO0 respectively~; high gloss Examples 34 and 36, which used PEG (M~ = 10,000), Example 35, which used PED0; and Example 38, which used P~D (MW =
nylon 66; or nylon 6/56 copolymer.
It has been observed th~t when a polyamide polymeric component is used, addition o~
an alkali or alkaline eaxth mstal salt alone will result in a composition displaying comparable antistatic properties to those realized by compositions employing the antistatic agent set forth above.
The antistatic agent may be incorporated into the thermoplastic polymeric component of the inventive antistatic thermoplastic composition by conventional melt blending techniques, such as reactive extrusion or mixing in a Banbury mixer where residual water is flashed off followed by a drying step just prior to feeding to a pelleti~ing device.
The antistatic agent may also be incorpor~ted into the thermoplastic polymeric component by copolymerizing the antistatic agent with copolymerizable monomers of the polymeric component. ~his is especially useful with polyamides.
In a preferred embodiment, the antistatic thermoplastic composition of the present invention is comprised of (1) from 95 to 80% by weight of acrylonitrile-butadiene styrene copolymer; and (2) from 5 to 20% by wei~ht of an antistatic agent comprising a3 from 99.9 to 90% by weight o~'amine ~unctionalized polyethylene oxide; and b) ~rom 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate.
3 ,~ 3 ~ ~
-~ o~-12-8889 In a more prefarred embodiment, the antistatic thermoplastic composition is comprised of (1) from 95 to 80% by weight of a styrenic polymer blend comprising a) from 98 to 80% by weight of acrylonitrile-butadiene-styrene copolymer; and b) ~rom 2 to 20% by weight of styrene-maleic anhydride copolymer, and 52~ from 5 to 20~ by weight of an antistatic agent comprising a) from 99.9 to 90% by weight of amine functionalized polyethylene oxide; and b) :Erom 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate. In the more preferred embodiment, ~t is further preferred that the mole ratio of free amine to anhydride in the inventive composition be about 1:5. It is believed that the reactive anhydride groups in the styre~e-maleic anhydride copolymer anchor the polyethylene oxide through the amine groups.
In another more pre~erred embodiment, the antistatic thermoplastic composition is co~prised of (1) from 95 to 80% by weight of nylon; and (2) from 5 to 20% by weight of an antistatic agent comprising (a) from 99.9% to 90% by weight of amine functionalized polyethylene oxide; and (b) from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate.
Other known additiYe~, such as impact modifiers, pigments, lubricants, stabilizsrs, fillers, antioxidants and flow aids may also be included in the antistatic thermoplastic compositions of the present invention provided such additives do not adversely affect the static'charge decay abilities of the resulting compositionO
In addition to th~ above description, the antistatic agent and antistatic thermoplastic composition of ths present invention are further ~ 3~3~
-7- 08~12-8~89 developed by reference to the illustrative, but not limiting, examples set forth below.
WO~ING EX~MP~ES
In the Working Examples s2t ~orth below, 5 the following components were used:
ABS - a rubber graft copolymer o~
butadiene and styrene (90/10% by weight) grafted with styrene and acrylonitrile wherein 65% by weight is styrene and 35% by weight i~
acrylonitrile. This intermecliate ABS was further diluted with styrene acrylonitrile copolymer as set forth below.
SAN - a copol~mer of 68% by weight based on the weight of the copolymer of styrene and 32% by weight o~
acrylonitrile.
SMAMMA - a copolymer of 68% by weight based on the weight of the copolymer of styrene; 25~ by weight of maleic anhydride; and 7% by weight of methylmethacrylate.
N6 - nylon 6 prepared as set ~orth herein.
PED ~mol. wt.] ~ polyether diaminas ~hich are predominantly polyethylene oxide with some polypropylene oxide sold by Texaco Chemical Company under the name Jeffamine~ ED series.
Bra~keted number denotes mole~ular weight.
PPP [mol. wt. range: E0% range] -polydimethylsiloxane carbinol terminated poly(ethylene oxide-2 ~
-8- 08~ 9 dimethylsiloxane-ethylen~ oxide~ ABA
block copolymer available from Huls America. Bracket~d numbers denote molecular weight range; ethylene oxide percentage range.
PE0 [mol. wt.J - polyethylene oxide available fro~ Union Carbide Company.
Bracketed number denotes molecular weight.
PED0 - polyether diol available from Union Carbide Company.
PEG [mol. wt.~ - polyethylene glycol available from Union Carbide Company.
Bracketed number denotes molecular weight.
PSSS - poly(styrene-4-sulphona~e) sodium salt svld by Scientific Polymer Products Company.
PAAS - poly(acrylic acid) sodium salt sold by Scientific Polymer Products Company.
MGS - magnesium stearate available ~rom C.P. Hall Co.
A-410 - ethoxylated alkyl amine sold by AXzo Chemie ~merica under the name Armostat 410.
A-C - a bis-ethylene diamine stearamide sold by Lonza Inc. under the name Acrawax C.
S~160 - n-butylbenzyl phthalate sold by Monsanto Chemical Company under the name Santicizer-160.
I-1076 - a hindered phenol type antioxidant sold by Ciba-Geigy Corp. under the name of Irganox 10'76.
, 3 3 ~
~-9~ 12-8889 CATALYST - a mayn~sium bromide caprolactam adduct with a melting point of abou~
70~C having a concen~ration of 1~0 mol~ of maynesium bromide per kilogram of caprolactam (21.6 wt. %
adduct; 78.4 wt. % caprolactam) - obtained from Grant Chemical Division of Ferro Corporation of Baton Rouge, Louisiana.
INITIATOR - iscphthaloyl biscaprolactam prepared by adding one (1) mole of bisacyldichloride to two (2~ mol~s of caprolactam. The ~ICl formed was neutralized with an amine and the product recovered.
The following laboratory r~agent grade chemicals were obtained from Aldrich Chemical Company and used without fur~her purification:
Lithium Chloride (LiCl) Lithium Acetate (LioAc) Lithium Carbonate (Li2Co3) Lithium Trifluoromethyl Sulphonate (LiCF3So3) Sodium Acetate (NaOAc) SAMPLE PREPARATIQN
The Working Examples set forth below, with the exception of the antistatic polyamide compositions, were prepared by compounding using a 3.4 kg. Banbury mixer. All solid intermediates including polymeric components and additives'such as antioxidants and flow aids were weighed and dry blended before adding to the Banbury mixer once the correct operating temperaturPs were reached.
(}
-10 08~ B889 Low molecular weight PEO additive~, having a molecular weight of less than or equal to 6000, which were generally waxy solids at room temperature, were pre-weigh~d inko glass jars and melted in a microwave oven just before addiny to the Banbury mixer.
Examples containing PED coordinated with alkali or alkaline earth metal salts were prepared by first dis601ving the salt as a 10 to 20%
solution in water and gradually adding this solution to mechanically stirred liquid PED, melted at 50 to 60C. The resulting aqueous PED/alkali or alkaline earth metal salt was then added to the dry blend in the Banbury mixer.
Working Examples containing polymeric sodium salts, poly(acrylic acid) and poly(styrene-4-sulfonate), were prepared by mixing these additives in with the dry blend in the Banbury mixer.
High gloss workiny examples which used high molecular weigh~ PEO (MW>6000) coordinated with an alkali or alkaline earth metal salt were prepared by mixing the PEO with the dry blend and adding an aqueous solution of 10 to 20% by weight alkali or alkaline earth metal salt directly to the Banbury mixer.
Set conditions for the Banbury mixer were ~s follows:
Circulating Oil Temperature 107C
Rotor Speed 100 rpm Ram Weight Air Pressur~ 0.41-0.55 MPa Post Flux Dump Time 60-80 ~ec.
Dump Temperature 215C
The compounded blends were dried thoroughly in a hot air ~irculating oven at 75 to 3~
~ 08-~2-8~89 80C for 24 hours or in a vacuum oven with a nitroyen bleed for 18 hours at the same temper-ature, prior to injection molding te~t specimens.
Molding was carried out on a 4 oz.
5 Arburg molding machine under the following general conditions-Zone 1 Temp., C 225 225 Zone 2 225 225 Zone 3 230 230 Nozzle Temp., C 230 230 Screw Speed, rpm 200 200 Injection Pressure, MPa 7.41 7.65 Mold Temp., C 120 120 .
The freshly molded specimens w~re conditioned for at least 24 hour~ at 23~C at 50%
relative humidity unless otherwise stated.
Examples 33 to 39 below illustrate the incorporation of the antistatic agent into a polyamide by copolymerization of a polyamide ~orming monomer with the metal salt complexes used as antistatic agents in th~ present invention. In Examples 33 to 38, caprolactam is used as the polyamide forming monomer while in Example 39, a combination o~ caprolactam and caprolactone is used to form a nylon copolymer having the antistatic agent as part of the copolymer backbone. When caprolactone is present it complexes with the metal salt, e.g. LiCl. The examples were prepared a~
~ollows: the metal salt was dissolved in water and an antistatic agent component ~i.e., PEO, PED;
PEDO; or PEG) was weighed out into a heated glass jar and then agitated on a magnetic stirring hot plate. During agitation, the metal salt/water solution was added and the resulting mixture 2~3~
-12- 08-12-88~9 agitated on the ma~netic stirring hot plate for 2 to 5 minutes. The mixture was then dried overnight in a vacuum oven at 90C under full vacuum. Hot molten caprolactam (<lOOppm moisture; mp = about 69C~ or caprolactone (distilled prior to u~e) was added to the dried mixture and the mixture maintained at between 110 and 130C until the caprolaotam or caprolactone wa~ dissolved. ~pon dissolution, thP initiator was added to form Reactant A.
In a second glass jar, caprolactam was weighed out and the catalyst dissolved therein to form Reactant B.
Reactant A and Reactant B were th~n mixed together and the resulting mixture poured into a 160~ stationary mold and allowed to polymPrize.
Polymerization times ranged from 5 to 7 minutes.
Test bars were routed from the resulting plaques and conditioned for at least 24 hours at 23C at 50~ relative humidity prior to testing.
TEST METHODS
The molded specimens and test bars were then subjected to the following tests:
Tensile properties - ASTM D636;
Flexural properties ~STM D790;
(Tensile and Flexural properties were measured o~
an Instron tester using 0.32 cm. tensile bars or 12.7 cm. x 1.27 cm. x 0.32 cm. bars.) Notched Izod Impact - ASTM D256;
HDTUL - ASTM D648 at 0.46 MPa fiber ~tress;
Vicat softening point - A5TM D1525 unde~ 1 Kg load;
Multiaxial Inverted ~art Impact ~IDI~ - The IDI determination utilized represents a modification of the test as described in 2~3 ~3~
-13 ~ ~ 12-88~9 Society of Plastics Engineers National Technical Conference l'Plastics in Surface Transportationl' Nov. 12-14, 1974, Detroit, Michigan, at page 238. In the modified test, instead o~ the dart being attached to the slider and striking the sample, the sample holder iæ aktached to the slider and strikes the instrumented dart. The rotary potentiometer is not used. The instrumented dart used is 1.2 cm. in diameter, and the sample strikes the instrumented dart at a velocity of 140.2 m/minO The samples were injection molded into 7.62 cm. x 10.2 cm. x 0.32 cm. plaques and then cut into two 5.08 cm. x 7.62 cm. piecss for testing.
Results are given in Joules (J).
Surface Gloss - measured using a Gloss Guard 11 device at an angle of 60;
% Charge Decay - a l'Static Honest Meter" was used to measure dissipation of electrostatic charge according to khe saturakion charged voltage. An electric charge was accumulated on the surface of the sample, until it reached a saturation voltage of 700v, by means o~ corona discharge. The discharge was then stopped and a sensing electrode used to record the surface electric charge decay with time in seconds. The % charge decay was then calculated from the data obtained at the specified time.
~ .3~7 -l4- OB-l2-8889 EXAMP1E5 Cl AND 1 TO 5 In thes0 Examples, molded specimens containiny PED and/or PPP and SMAMMA were tested for mechanical strength and static decay properties. The results ~re tabulated in Table I.
3 ~ 3 l~
SUM~ARY 0~ EX~MPLES C-l_A~ 1 qD 5 E~MP1~ C-1* 1 2 3 4 5 oo~PQNENTS (% by weight) SAN 6~ 50 50 50 50 ~0 SM~MM~ _ - 15 15 15 _ 15 ~15 _ (E~) PED [6000] - 5 10 - - 5 PPP [2200-2600, - - - 5 10 5 45-55%J
A-C 0.8 0.8 0.8 0~8 0.80.8 I-1076 _0.2 0.2 0.2 0.2 0020.2 PRf)~ES
Tensile Str (MPa)44.4 37 32.1 34.128.9 26.7 Iensile ~d (Gæa) 2.7 2.3 2.4 2.52.3 2.1 ElQngation (%)6 42 83 23 6 5 IDI Emax (J)4.7 9.2 23.1 6.6 5.4 11 Efail (J~5.2 3.5 37.6 7.2 6.212.8 Izod Impact 211.89.6 26.8 7.5 6.711.7 Notched (KJ/m ) (MB) (NB) ~DqUL ( C) 84 89 87 86 81 8~
~ica~, IK3 ( C) 103 112 111 108104 107 % Charge Decay at T = lOs.10 4 50 31 34 4 * C 1 oontains 1~ by weight o~ ~-410.
NB = Not broken.
2 ~ 3~' -16- 0~12 ~8 Examples 1 to 5 demonstra~e ~he ef~ect o~
adding PED and/or PPP to an ABS/S~MMA blend.
Example 1 which incorporated PED and SMAMMA, although able to e~fect static decay, showe~ no static decay improvement over the Control C~1 which utilized the priox art antistatic agent, A-410, in the absence of SMAMNA. Example 2, in which the amount of PED was increased from 5 pph to 10 pph, as compared to Example 1, showed a substantial improvement in its ability to achieve fast static charge decay in addition to showing a substantial improvement in both IDI and notched Izod ~no break in 7.62 cm. bars) impact properties.
There was little change in the tensile modulus and heat (HDTUL at 87C) ~f Example 2 as compared to Example l. Examples 3 and 4, which utilized 5 pph and 10 pph PPP respectively, demonstrated a similar ability to achieve fast static charge decay, as compared to Examples 1 and 2, although the resultank resin showed slightly lower impact properties.
Example 5 which incorporated 5 pph each of PED and PPP along with SMAMMA also demonstrated an ability to achieve static charge decay and demonstrated improved impact properties as compared to Examples 3 and 4.
In Examples C-2 and 6 to 1~, molded specimens containing varying amounts of SAN, SM~MMA
and PED were tested. The re~ults are set forth in Table II. I
~ ~ g ~
I!~E II
St~RY OF EX1~ C-2 AND ~ TO 10 EXP.M~C--2 6 7 8 9 1 ~ = (~ by wei~jht) A~S 35 35 35 35 35 35 SPN 5~ 55 60 ~5 55 55 VE~ (PE h) P~D t6000] - 10 8 10 15 20 10 A-C 0.8 0.8 0.8 0~8 0.8 0.8 I-1076 0.2 0.2 0.2 0.2 0.2 0.2 % M~ noles/100 g) 26 26 13 %-NH2 (~ ~les) 0 3.3 2.6 Ratio M~/-NH~ _- 7.9 4.9 15 PRf)PEgIl~S
Tensile St~ (MPa) 49.329~6 30.5 29.9 27.2 21.8 Tensile M~d (OE'a) 2.8 2.4 2.5 2.1 2.1 1.7 El~gation (%) 7 97 112 92 55 78 IDI Emax (J) 1.3 14.520.6 16.7 18.5 11.6 20 Eeail (J) 1.4 20.933.5 252g.4 14.a~
Izod ~act 2 3 26 26 28.1 25.8 22.7 Nc~tched (XJ/m ) HD~ (C) 91 85 8~ 83 82 ND
Vicat, 1~ (C) 112 109 108107 106 ND
25 % C~an3e Decay at T = lOOs. 0~28 26 27 61 48 90 ND = Not De~mi~.
~a~33~
-18- OB-12~8889 Examples 6 and 7 demonstrate the effect of varying the amounts of SAN, SMAMMA and PED in the blend. In particular, these Examples show the best combination of these components or the best mole ratio o~ free amine to anhydride in the blend in terms of achieving optim~m mechanical properties.
From the r~sults set forth in TabIe II, it appears that the best combination of impact, heat and modulus is obtained in Example 7 with 5%
SMAMMA and 8pph PED with a mole ratio of free amine to anhydride in the blend of approximately 1-5.
Examples 8 to 10 show the effect of increased amounts of PED on the mechanical properties of the blend. From the results set forth in Table II, it appears that although increased amounts of PED in the ABS/SMAMMA blend typically improve the blends static charge decay ability amounts in excess of 15 pph adversely affect the blends mechanical properties.
In these Examples, th~ effect of lithium chloride addition on the molded specimens' mechanical strenqth and static decay properties were measured. The results are tabulated in Table IIIo In Examples 15 to 21, the amounts of each additive are expressed as parts per hundred parts of the polymeric component.
2~3~
-19-- 08- 12 -88~9 rJ ~
,~ ~ o In u~ ~ o I ~ c ~ o~ x o~
o o ~ ~ i o ,~ c lY ~ ~ 1 ~1 ,~ ~ ~ o~ ~
~I o In x o In u~ o i~ o ,~ o ~o co ~ I
~1 r~ ~ ~1 ,1 r~
~r ~ I~ OD
O 1` 0 ~J O
~1 ~1 U~ l`
~ ~ u~ o m o r~ o ~ o u~
1~ ~ u~ ~
~ ~ ~ a~1 ~ O O ~ CO a~ ~1 Hl t~ ~n~1 0 HC~ lf) CO ~
~ ~ ~ ~ o o ~ ~ ~ 1 o ô d' C~
~1 f'~ In OD U~
u~ m r o ~ a ~ ~y ~1 ~ u~ o o s: r~ ~ o o~
~Ul ;~
~ ~1 o o 1` ~ ~i ~
~ ~ o ~
'~
?~ ?~
2~ ~33~
Examples 11 to 15, prepared by incorporating LiCl, suspended in PED, in with the ABS/SMAM~A blend in a Banbury mixer, demonstrate the e~fect of LiCl addition on the resulting blendsl static charge decay ability~
Examples C 3 and 11, as set forth in Table III, show that the addition of LiCl suspended in PED to the ABS/S~AMMA blend results in an improvement in static charge decay ability.
lQ Examples C3 to 14 demonstrate that as the % LiCl level increased from 0 to 1.5%, khe static charge decay ability also increased~ Examples 13 and 15 show that increasing the amount of PED favorably affects the static charge decay ability and does not affect the matPrials impact properties. It was observed that materials molded from the blends with higher salt contents showed phase separated crystals of LiCl on the surface. This may account for the improved ~tatic charge decay and the lower observed impact strengths of these materials.
Examples 16 to 20 show the effect of using the preferred preparation method initially set ~orth and varying the amounts o~ polymeric component levels on the resulting materials impact strength.
Examples 16 to 20 demonstrate, in general, that preparation of these blends according to the preferred preparation method, in comparison to the method outlined for Examples 11 to 15 above, favorably effects the r~sulting materials Xzod strength. Examples 16 to 18 show that decreasing the ABS level understandably results in slig~tly decreased Izod strengths. Example 19, in comparison to Example 17, and Example 20, in comparison to Example 18, demonstrate that s~
~ 0~ 8889 increased levels of P~D and ~iCl also result in ~lightly decreased Izod ~tr~ngths.
~ xample 21 represents an optimized blend that demonstrates good mechanical properties and notable % Charge Decay at T = lOs. Example 21 incorporates S-160 instead of A-C plasticizer.
In Examples C-4 and 22 to 24, certain polymeric salt~ were evaluated in place of LiCl according to the formulations set forth below in Table IV.
~,3~C3~
~I r~ ~! 'P tn ~ 111 O 11~ 1~ 1 Itl ~ t~l O ~ 11~ 1~ r~
t`i 1 ~D rl N N
d ~
~ ~ Itl O In ~ d' ~
) t~ 1~1 O 1~1 In N I d' t~ ~ d' t~ rl rl t~ ~ ~o r~ ~ ~t 00 ~ ~D
rl u~ o In In I I ~ ~ ~
_ r-l ~r~ Ul rl N r1 OD rl ~ ~ ~ ~p ~ ~ , _ h ~
In o 2 0 ~ 3 ~ 3 ~3- oa-l2-~889 Examplas 22 to 24, in comparison to Control C-4, demonstrate that both polymeric salts utilized are success~ul in effecting rapid charge decay. Although the impact properties o~ these materials was decreased, these properties are still within acceptahle limits for some applications.
~IPL~S C--5 A~ 2 5 '10 2 8 In Examples C-5 and 25 to 28, several alternative salts were evaluated in place of hiCl.
The results are tabulated în Table V~
~ ~ ~ O ~3~ c'~ () --2~-- 08--~2~888~
~ In ~
co u~ o u~ ~ ~! o ~r ~ ~ G~ r~ ~ ~ a~ ~ ~ t~
~ 1` ~D rl ~ N ~ ~ ~I N~ t~ ~
~) I
~` 1~ 0 l~ ~ 1~ r-i cn o X '~
g ~ ~ o~
1~ U) ~ ~1~ ¦ ~ cn ~') ~i NN 1` ~ 1`
P ~
In ~ o ~ ~ ~ o ~P ~i o ~ ;i o ~D ~ ~ tl1 0 ~ ~ O~
~n ~3 ~ O c~
__ ~ _ O U~.
20($(~33~, -25- ~8-12 888~
Examples 25 to 28 demonstrate the ability of salts other than LiCl to ef ~ect comparable static decay while maintaining or improving the resultant blends~ mechanical properties. Most notable is Example 27, which incorporates likhium trifluoromethyl ~ulphonate ~triflat~) salt, and which demonstrates comparable % Charge Decay as in Control C-5 utilizing LiCl, but which results in a blend with improved impact strength.
EXAMPLES C-6 ~ND 29 TO 32 In Examples C-6 and 29 to 32, high molecular weight PED's complexed with LiCl were used in melt blends with ABS/SMAMMA to achieve antistatic materials with high surface gloss~ The results are tabulated in Tabl~ VI.
2f~(3~3 -33~
-26- 08-12-~89 ~I U) 11) 0 1~ o N O N ~ ~D ~ D
u~ ~
~1 u~ o u~ r~ o r~ D 0 ~D In r~ I r1 QO 0~ 03 ~ In O In O It~ ~ O ~ t`' N L~ r` O ~r 1~ 1` ~1 al r~ t~7~O ~1 l U~
~ C~ 0~ 1~ 0 U~ ~ O O ~ N 1~ ~r ~ W OD 11~ ~r ~ OD
~ ~ç3 1~ ~ D ~_1 ~ !~
~ ~ lO O u1 ~ o tO r- N ~) N ~ CO N 11~ ~
_ , ,~
.~ _ ~
,~
o ~1 ~1o~ ~ 3 ~ ~ ~1 ~ @ ~ ~1 o o In o u~
~ ,, 2 Q (~ ~ t) rl (~
-27- ~8~ 8B89 5ignificant % Charge Decay at T a 5 seconds was demonstrated in Control C-6 and in Example~ 29 to 32.
Control C 6 which utilized a P~D having a molecular weight of 6000 produced a material having inherently low surface gloss. In comparison, Examples 29 and 31 which utilized PEDIs having molecular weights o~ 12,000 and 100,000 respectively demonstrated increased surface gloss lo while Example 30 which utilized a 50/50 mix of 300/600K PED achie~ed a ~ery high gloss of 94%. In addition, the mechanical strength (flex and tensile), the IDI and notched Izod impact strengths and the thermal properties of Example 30 were improved over Control C-6. Examples 31 and 32 show that the absence of SMAMMA in the inventive "high gloss" composition increases the % gloss, but lowers the % Elongation and IDI strength.
In Examples 33 to 38, test bars of antistatic nylon 6 homopolymer compositions containing PED, PEG, PE0, or PED0 and lithium chloride were tested for static charge decay abilities. In Example 39, a test bar of a nylon 6 copolymer containing about 11.7% by weight of caprolactone composition that employed lithium chloride was also tested for static charge decay abilities.
3 3 ~
~8~ 0~ 12-8~89 T~E~VII
S~RX OF EX~E~ 33 TO 39 E~ E 33 34 35 36 37 38 39_ coM~In~ns (% by weight) N6 100 100_ 1OO 100 100 lOQ 8 ~ 7 PED [6000] ~ 13.2 PEG [lO,OGO] - 13.2 ~ 26.3 PE~ ~300,000] 6.1 ~
PE~ [lQO,OOO] - - - - 6.1 PEDO - - 13.2 - - - -LiCl 1.4 1.4 1.4 1.4 1.4 1.4 1.4 I~n~OR 2.1 2.1 2.1 2.1 2.1 2.1 2.1 CAr~YST 15.8 15.~ ~5.8 15.8 15.8 15.8 15 8 PRQP ~lES
% o~e Decay a~ T = ~Os. 83.1 100 89.1 100 100 100 100 * Contains 88.3% by weight caprolactam and 11.7% by weight caprolactone.
2 f~
~29- 08-12-8~B9 In high glo65 Examples 33 and 37, which used high molecular weight PEO (MW = 300,000 and MW
= lOO,oO0 respectively~; high gloss Examples 34 and 36, which used PEG (M~ = 10,000), Example 35, which used PED0; and Example 38, which used P~D (MW =
6,000); all of which used LiCl and a nylon 6 polymeric component resulted in compositions with comparably high static charge decay abilitles.
Example 39 demonstrates that, in nylon 6 copolymer compositions, lithium chloride addition alone is sufficient to effect rapid static charge decay in the resulting composition.
These Examples, which are included here for comparison purposes, illustrate compositions which do not exhibit the static charge decay abilities obtained with the compositions of the present invention. The molded specimens were prepared according to the compounding method. The compositions and their charge decay properties are set forth in Table VIIIo ~ ~ ~J 3 ~
--30-- 08--12--88~9 ~ VIII
Sl~ OF OCMPA~V~ EXP~ 40 TO 41 EX~ _ . _ 40 4 QaP~PCNE~ (% ~ ht) AB~ 35 35 S~N 60 60 5M~7A 5 5 P~ [300, oo~] 12 12 ~S O . 55 2 . 5 A~ 0.5 0.5 S-~60 o. 5 o . 5 I-1076 _ O . 2 0. 2 E~P~rl:ES
% C~arge Decay at T = lOs.14.7 17.2 2 ~ 3 ~:~ g Comparative Examples 40 to 41 demonstrats that the use of 0.55 and 2.5 pph magnesium stearate respectively, in combination with non-~unctionalized polyethylene oxide, as an antistatic agent in a styrenic polymer blend, results in compositions displaying markedly reduced static charge decay abilities. This may be due in part to the inability of magnesium stearate to complex with polyethylene oxide.
Example 39 demonstrates that, in nylon 6 copolymer compositions, lithium chloride addition alone is sufficient to effect rapid static charge decay in the resulting composition.
These Examples, which are included here for comparison purposes, illustrate compositions which do not exhibit the static charge decay abilities obtained with the compositions of the present invention. The molded specimens were prepared according to the compounding method. The compositions and their charge decay properties are set forth in Table VIIIo ~ ~ ~J 3 ~
--30-- 08--12--88~9 ~ VIII
Sl~ OF OCMPA~V~ EXP~ 40 TO 41 EX~ _ . _ 40 4 QaP~PCNE~ (% ~ ht) AB~ 35 35 S~N 60 60 5M~7A 5 5 P~ [300, oo~] 12 12 ~S O . 55 2 . 5 A~ 0.5 0.5 S-~60 o. 5 o . 5 I-1076 _ O . 2 0. 2 E~P~rl:ES
% C~arge Decay at T = lOs.14.7 17.2 2 ~ 3 ~:~ g Comparative Examples 40 to 41 demonstrats that the use of 0.55 and 2.5 pph magnesium stearate respectively, in combination with non-~unctionalized polyethylene oxide, as an antistatic agent in a styrenic polymer blend, results in compositions displaying markedly reduced static charge decay abilities. This may be due in part to the inability of magnesium stearate to complex with polyethylene oxide.
Claims (30)
1. An antistatic agent, for use in thermoplastic polymers, which comprises a functionalized alkylene oxide polymer selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, copolymers of ethylene oxide and propylene oxide, and polydimethylsiloxane carbinol terminated poly(ethylene oxide-dimethylsiloxane-ethylene oxide) ABA block copolymers and blends thereof, wherein the functional group of the functionalized alkylene oxide polymer is selected from the group consisting of hydroxy, epoxy and amino groups; and optionally a minor amount of an alkali or alkaline earth metal salt capable of complexing with the functionalized alkylene oxide polymer.
2. The anitstatic agent of Claim 1 wherein the antistatic agent is a functionalized alkylene oxide polymer.
3. The antistatic agent of Claim 1 which comprises:
a. from 99.9 to 90% by weight of a functionalized alkylene oxide polymer; and b. from 0.1 to 10% by weight of an alkali or alkaline earth metal salt capable of complexing with the functionalized alkylene oxide polymer;
wherein the sum of components (a) and (b) total 100% by weight.
a. from 99.9 to 90% by weight of a functionalized alkylene oxide polymer; and b. from 0.1 to 10% by weight of an alkali or alkaline earth metal salt capable of complexing with the functionalized alkylene oxide polymer;
wherein the sum of components (a) and (b) total 100% by weight.
4. The antistatic agent of Claims 1, 2 or 3 wherein the functional group of the functionalized alkylene oxide polymer is an amino group.
5. The antistatic agent of Claims 1, 2 or 3 wherein the alkylene oxide polymer is polyethylene oxide.
6. The antistatic agent of Claim 5 wherein the polyethylene oxide has a molecular weight of greater than 100,000.
7. The antistatic agent of Claims 1 or 3 wherein the metal salt is lithium chloride or lithium trifluoromethyl sulphonate.
8. The antistatic agent of Claim 3 which comprises:
a. from 99.9 to 90% by weight of amine functionalized polyethylene oxide; and b. from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate;
wherein the sum of components (a) and (b) total 100% by weight.
a. from 99.9 to 90% by weight of amine functionalized polyethylene oxide; and b. from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate;
wherein the sum of components (a) and (b) total 100% by weight.
9. An antistatic agent, for use in thermoplastic polymers, which comprises:
a. from 99.9 to 90% by weight of an alkylene oxide polymer selected from the group consisting og polyethylene oxide, polypropylene oxide, polybutylene oxide, copolymers of ethylene oxide and propylene oxide, and polydimethylsiloxane carbinol terminated poly(ethylene oxide-dimethylsiloxane-ethylene oxide) ABA block copolymers and blends thereof; and b. from 0.1 to 10% by weight of an alkali or alkaline earth metal salt capable of complexing with the alkylene oxide polymer;
wherein the sum of components (a) and (b) total 100% by weight.
a. from 99.9 to 90% by weight of an alkylene oxide polymer selected from the group consisting og polyethylene oxide, polypropylene oxide, polybutylene oxide, copolymers of ethylene oxide and propylene oxide, and polydimethylsiloxane carbinol terminated poly(ethylene oxide-dimethylsiloxane-ethylene oxide) ABA block copolymers and blends thereof; and b. from 0.1 to 10% by weight of an alkali or alkaline earth metal salt capable of complexing with the alkylene oxide polymer;
wherein the sum of components (a) and (b) total 100% by weight.
10. The antistatic agent of Claim 9 wherein the alkylene oxide polymer is polyethylene oxide.
11. The antistatic agent of Claim 9 wherein the metal salt is lithium chloride or lithium trifluoromethyl sulphonate.
12. The antistatic agent of Claim 9 which comprises:
a. from 99.9 to 90% by weight of polyethylene oxide; and b. from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate;
wherein the sum of components (a) and (b) total 100% by weight.
a. from 99.9 to 90% by weight of polyethylene oxide; and b. from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate;
wherein the sum of components (a) and (b) total 100% by weight.
13. An antistatic agent, for use in thermoplastic polymers, which comprises:
a. from 99.9 to 90% by weight of amine functionalized polyethylene oxide; and b. from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate;
wherein the sum of components (a) and (b}
total 100% by weight.
a. from 99.9 to 90% by weight of amine functionalized polyethylene oxide; and b. from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate;
wherein the sum of components (a) and (b}
total 100% by weight.
14. An antistatic thermoplastic composition comprising:
a. from 95 to 80% by weight of a thermoplastic polymeric component; and b. from 5 to 20% by weight of an antistatic agent which comprises a functionalized alkylene oxide polymer selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, copolymers of ethylene oxide and propylene oxide, and polydimethylsiloxane carbinol terminated poly(ethylene oxide-dimethylsiloxane-ethylene oxide) ABA block copolymers and blends thereof, wherein the functional group of the functionalized alkylene oxide polymer is selected from the group consisting of hydroxy, epoxy and amino groups; and optionally a minor amount of an alkali or alkaline earth metal salt capable of complexing with the functionalized alkylene oxide polymer;
wherein the sum of components (a) and (b) total 100% by weight.
a. from 95 to 80% by weight of a thermoplastic polymeric component; and b. from 5 to 20% by weight of an antistatic agent which comprises a functionalized alkylene oxide polymer selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, copolymers of ethylene oxide and propylene oxide, and polydimethylsiloxane carbinol terminated poly(ethylene oxide-dimethylsiloxane-ethylene oxide) ABA block copolymers and blends thereof, wherein the functional group of the functionalized alkylene oxide polymer is selected from the group consisting of hydroxy, epoxy and amino groups; and optionally a minor amount of an alkali or alkaline earth metal salt capable of complexing with the functionalized alkylene oxide polymer;
wherein the sum of components (a) and (b) total 100% by weight.
15. The antistatic thermoplastic composition of Claim 14 wherein the polymeric component is selected from the group consisting of styrenic polymers, polyamides, polycarbonates, polyolefins, polyureas, polyurethanes and blends thereof.
16. The antistatic thermoplastic composition of Claim 15 wherein the polymeric component is a styrenic polymer.
17. The antistatic thermoplastic composition of Claim 16 wherein the styrenic polymer is selected from the group consisting of polystyrene, styrene acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers acrylonitrile-styrene-acrylate copolymers, methacrylate-butadiene-styrene copolymers, styrene-maleic anhydride copolymers, styrene-methyl methacrylate copolymers, styrene-maleic anhydride-methyl methacrylate copolymers and blends thereof.
18. The antistatic thermoplastic composition of Claim 15 wherein the polymeric component is a polyamide.
19. The antistatic thermoplastic composition of Claim 18 wherein the polyamide is selected from the group consisting of homopolymers including nylon 6, nylon 66, nylon 4, nylon 8, nylon 11, nylon 12, nylon 69, nylon 610, and nylon 612 and copolymers including nylon 6/66, nylon 6/12, nylon 6/69, and lactam-lactone copolymers.
20. The antistatic thermoplastic composition of Claim 14 wherein the antistatic agent is a functionalized alkylene oxide polymer.
21. Tha antistatic thermoplastic composition of Claim 14 wherein the antistatic agent comprises:
a. from 99.9 to 90% by weight of a functionalized alkylene oxide polymer; and b. from 0.1 to 10% by weight of an alkali or alkaline earth metal salt capable of complexing with the functionalized alkylene oxide polymer;
wherein the sum of components (a) and (b) total 100% by weight.
a. from 99.9 to 90% by weight of a functionalized alkylene oxide polymer; and b. from 0.1 to 10% by weight of an alkali or alkaline earth metal salt capable of complexing with the functionalized alkylene oxide polymer;
wherein the sum of components (a) and (b) total 100% by weight.
22. The antistatic thermoplastic composition of Claim 17 which comprises:
a. from 95 to 80% by weight of an acrylonitrile-butadiene-styrene copolymer; and b. from 5 to 20% by weight of an antistatic agent comprising:
i. from 99.9 to 90% by weight of amine functionalized polyethylene oxide;
and ii. from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate;
wherein the sum of components (i) and (ii) total 100% by weight; and wherein the sum of components (a) and (b) total 100% by weight.
a. from 95 to 80% by weight of an acrylonitrile-butadiene-styrene copolymer; and b. from 5 to 20% by weight of an antistatic agent comprising:
i. from 99.9 to 90% by weight of amine functionalized polyethylene oxide;
and ii. from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate;
wherein the sum of components (i) and (ii) total 100% by weight; and wherein the sum of components (a) and (b) total 100% by weight.
23. The antistatic thermoplastic composition of Claim 17 which comprises:
a. from 95 to 80% by weight of a styrenic polymer blend comprising:
i. from 98 to 80% by weight based on the total weight of the blend of acrylonitrile butadiene-styrene copolymer; and ii. from 2 to 20% by weight based on the total weight of the blend of styrene-maleic anhydride copolymer, wherein the sum of components (i) and (ii) total 100% by weight; and b. from 5 to 20% by weight of an antistatic agent comprising:
i. from 99.9 to 90% by weight of amine functionalized polyethylene oxide;
and ii. from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulfonate;
wherein the sum of components (i) and (ii) total 100% by weight; and wherein the sum of components (a) and (b) total 100% by weight.
a. from 95 to 80% by weight of a styrenic polymer blend comprising:
i. from 98 to 80% by weight based on the total weight of the blend of acrylonitrile butadiene-styrene copolymer; and ii. from 2 to 20% by weight based on the total weight of the blend of styrene-maleic anhydride copolymer, wherein the sum of components (i) and (ii) total 100% by weight; and b. from 5 to 20% by weight of an antistatic agent comprising:
i. from 99.9 to 90% by weight of amine functionalized polyethylene oxide;
and ii. from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulfonate;
wherein the sum of components (i) and (ii) total 100% by weight; and wherein the sum of components (a) and (b) total 100% by weight.
24. The antistatic thermoplastic composition of Claim 23 wherein the mole ratio of free amine to anhydride is about 1:5.
25. The antistatic thermoplastic composition of Claim 19 which comprises:
a. from 95 to 80% by weight of nylon 6; and b. from 5 to 20% by weight of an antistatic agent comprising:
i. from 99.9 to 90% by weight of amine functionalized polyethylene oxide;
and ii. from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate;
wherein the sum of components (i) and (ii) total 100% by weight; and wherein the sum of components (a) and (b) total 100% by weight.
a. from 95 to 80% by weight of nylon 6; and b. from 5 to 20% by weight of an antistatic agent comprising:
i. from 99.9 to 90% by weight of amine functionalized polyethylene oxide;
and ii. from 0.1 to 10% by weight of lithium chloride or lithium trifluoromethyl sulphonate;
wherein the sum of components (i) and (ii) total 100% by weight; and wherein the sum of components (a) and (b) total 100% by weight.
26. The antistatic thermoplastic composition of Claim 14 wherein the antistatic agent is added to the polymeric component during a melt blending process.
27. The antistatic thermoplastia composition of Claim 14 wherein the antistatic agent is copolymerized with copolymerizable monomers of the polymeric component.
28. An antistatic thermoplastic composition comprising:
a. from 95 to 80% by weight of a polyamide; and b. from 5 to 20% by weight of an antistatic agent which comprises an alkali or alkaline earth metal salt;
wherein the sum of components (a) and (b) total 100% by weight.
a. from 95 to 80% by weight of a polyamide; and b. from 5 to 20% by weight of an antistatic agent which comprises an alkali or alkaline earth metal salt;
wherein the sum of components (a) and (b) total 100% by weight.
29. The antistatic thermoplastic composition of Claim 28 wherein the polyamide is selected from the group consisting of homopolymers including nylon 6, nylon 66, nylon 4, nylon 8, nylon 11, nylon 12, nylon 69, nylon 610, and nylon 612 and copolymers including nylon 6/66, nylon 6/12, nylon 6/69 and lactam-lactone copolymers.
30. The antistatic thermoplastic composition of Claim 29 which comprises:
a. from 95 to 80% by weight of a caprolactam-caprolactone copolymer; and b. from 5 to 20% by weight of lithium chloride or lithium trifluoromethyl sulphonate;
wherein the sum of components (a) and (b) total 100% by weight.
a. from 95 to 80% by weight of a caprolactam-caprolactone copolymer; and b. from 5 to 20% by weight of lithium chloride or lithium trifluoromethyl sulphonate;
wherein the sum of components (a) and (b) total 100% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82744092A | 1992-01-29 | 1992-01-29 | |
| US07/827,440 | 1992-01-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2088338A1 true CA2088338A1 (en) | 1993-07-30 |
Family
ID=25249229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002088338A Abandoned CA2088338A1 (en) | 1992-01-29 | 1993-01-28 | Anti-static agent for thermoplastic polymers |
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| Country | Link |
|---|---|
| US (1) | US5346959A (en) |
| EP (1) | EP0555197A3 (en) |
| JP (1) | JP2662158B2 (en) |
| CA (1) | CA2088338A1 (en) |
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| KR20040052125A (en) * | 2002-12-13 | 2004-06-19 | 서광석 | Polystyrene compounds for conductive coating and anti-static polystyrene sheets |
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| US20100175555A1 (en) * | 2008-09-12 | 2010-07-15 | Ismael Ferrer | Polyamide Fine Fibers |
| US8468968B2 (en) | 2009-10-22 | 2013-06-25 | Quest Inspar LLC | Method and apparatus for lining pipes with isocyanate and hydroxyl-amine resin based on castrol or soy oil |
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| KR101336838B1 (en) * | 2012-05-15 | 2013-12-04 | 이용수 | Colorless antistatic agent for electronic materials, menufactruirng method of it and ultraviolet-curable antistatic coating agent using the antistatic agent, coating material using it |
| US9265648B2 (en) * | 2012-05-15 | 2016-02-23 | Hollister Incorporated | Odor barrier film |
| CN103910856B (en) * | 2013-01-08 | 2016-06-08 | 深圳市景江化工有限公司 | Nonionic waterborne epoxy curing agent and its preparation method |
| CN107406537B (en) | 2015-03-26 | 2019-08-20 | 巴塞尔聚烯烃股份有限公司 | Polymerization technique in the presence of antistatic agent |
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| DE1570605A1 (en) * | 1965-09-15 | 1970-02-05 | Bayer Ag | Hydrophilic, thermally stable polyester amides with sulfonic acid groups |
| US3591565A (en) * | 1967-10-06 | 1971-07-06 | Du Pont | Polyamides containing alkali metal halide additives as void formation inhibitors |
| JPS497574B1 (en) * | 1970-12-14 | 1974-02-21 | ||
| CH569076A5 (en) * | 1972-08-22 | 1975-11-14 | Sandoz Ag | |
| JPS5380497A (en) * | 1976-12-27 | 1978-07-15 | Toray Ind Inc | Preparation of block polyetheramide composition |
| JPS541362A (en) * | 1977-06-07 | 1979-01-08 | Teijin Ltd | Antistatic polyester composition |
| JPS59142242A (en) * | 1983-02-04 | 1984-08-15 | Toray Ind Inc | Resin composition having excellent antistatic property |
| JPS59142243A (en) * | 1983-02-04 | 1984-08-15 | Toray Ind Inc | Antistatic resin composition |
| JPS59192718A (en) * | 1983-04-12 | 1984-11-01 | Asahi Chem Ind Co Ltd | Antistatic polyester conjugated fiber |
| JPS59192719A (en) * | 1983-04-12 | 1984-11-01 | Asahi Chem Ind Co Ltd | Antistatic polyester fiber |
| GB2139230A (en) * | 1983-05-04 | 1984-11-07 | Kokoku Rubber Ind | An electrically conductive high-molecular composition |
| JPS61261359A (en) * | 1985-05-15 | 1986-11-19 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
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| CA1318740C (en) * | 1987-04-17 | 1993-06-01 | Simon Hsiao-Pao Yu | Copolymers of ethylene oxide as antistatic additives |
| US5077330A (en) * | 1988-08-29 | 1991-12-31 | Armstrong World Industries, Inc. | Conductive polyurethane-urea/polyethylene oxide |
| JPH03122165A (en) * | 1989-10-06 | 1991-05-24 | Japan Carlit Co Ltd:The | Electroconductive resin composition |
| CA2032313A1 (en) * | 1989-12-21 | 1991-06-22 | Simon Hsiao-Pao Yu | Additive for imparting electro-static dissipative properties in plastic materials and method relating thereto |
| WO1991009906A1 (en) * | 1990-01-05 | 1991-07-11 | The B.F. Goodrich Company | Chain extended low molecular weight polyoxiranes for electrostatic applications |
| JPH03239745A (en) * | 1990-02-19 | 1991-10-25 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition |
| US5188783A (en) * | 1990-02-20 | 1993-02-23 | Hughes Aircraft Company | Method of making articles containing an ion-conductive polymer |
| JPH04114061A (en) * | 1990-09-03 | 1992-04-15 | Asahi Chem Ind Co Ltd | Highly heat-resistant resin composition |
-
1993
- 1993-01-28 EP EP19930870017 patent/EP0555197A3/en not_active Withdrawn
- 1993-01-28 CA CA002088338A patent/CA2088338A1/en not_active Abandoned
- 1993-01-28 JP JP5012599A patent/JP2662158B2/en not_active Expired - Lifetime
- 1993-07-21 US US08/095,291 patent/US5346959A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US5346959A (en) | 1994-09-13 |
| EP0555197A3 (en) | 1993-11-18 |
| EP0555197A2 (en) | 1993-08-11 |
| JP2662158B2 (en) | 1997-10-08 |
| JPH07247413A (en) | 1995-09-26 |
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