CA2238265A1 - Polymeric compositions - Google Patents
Polymeric compositions Download PDFInfo
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- CA2238265A1 CA2238265A1 CA002238265A CA2238265A CA2238265A1 CA 2238265 A1 CA2238265 A1 CA 2238265A1 CA 002238265 A CA002238265 A CA 002238265A CA 2238265 A CA2238265 A CA 2238265A CA 2238265 A1 CA2238265 A1 CA 2238265A1
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- Prior art keywords
- composition
- weight
- treating agent
- polymer
- filler material
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Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
- Y10T428/2942—Plural coatings
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
- Y10T428/2942—Plural coatings
- Y10T428/2947—Synthetic resin or polymer in plural coatings, each of different type
Abstract
A composition comprising an ehtylene containing polymer, a cross-linking agent and a treated filler material. The treated filler material comprises a treating agent which is a polymer comprising acrylonitrile and at least one other monomer. A preferred treated filler material is a treated carbon black and a preferred ethylene containing polymer is an ethylene vinyl acetate (EVA) polymer. A semiconductive composition of the present invention may be advantageously utilized in electrical wire and cable application.
Description
CA 0223826~ 1998-0~-21 POJ.YMFR~C C~OMPOSITIQNS
Field of the Invention The present invention relates to a composition co~ illg a treated filler material, pler~,.dbly a treated call~unaceous filler material, a crosslinking agent and a ethylene cont~ining polymer. A ~ r~,llcd treated filler material co~ l;ses earbon black and ~ f~ d ethylene eont~ining polymers are ethylene-vinyl acetate (EVA), ethylene-propylene (EPR) and ethylene propylene diene monomer (EPr)M).
R~r~olln~l ofthe Jnvention The treating of earbon black with polymeric binders is disclosed in the art.
Previous patents disclose the art of incoll~uldlillg additives to produee pelletized treated filler materials, in partieular pelletized treated carbon blacks, with improved handling cllala~ .; ,Lics, for example, low dust.
The eonstruction of inc~ ted electrical conduetors, i.e., wire and cables designed for medium and high voltage applic~tionc, is known in the art. Typical constructions inelude a eore eonduetor whieh eomprises one or more strands of a eondueting metal or alloy such as copper or alllminllm; a layer of a semiconclurtive shielding compound; a layer of inclll~tion such as cr~ cclinked polyethylene or ethylene-propylene rubber and a layer of a semiconductive insulation shield compound overlaying the insulation.
The conductor shield, the insulation shield and the overlaying semicûnductive shield layer may be formed by either a two pass or by a single pass triple extrusion proeess. ~ two pass operation refers to a process whereby the conductor shield and the jncnl~tiQn layer are extruded in tandem and then crosslinked prior to extrusion of the semieonduetor insulation layer. A single pass triple extrusion process refers to a process in which the conductor shield, the insulation layer and the semiconductive shield are all extruded in a eommon extrusion head and crosclinkPd simultaneously. The single pass triple extrusion process minimi7~s production steps and hence is a plc:felltid method of m~nnf~chlre~ However, the single pass triple extrusion process generally makes the semiconductive shield layer more fully bonded to the insulation layer, than in a two pass operation.
Generally, in order to splice incul~ted electrical wires, or make terminal connections, the semiconductive shield layer should be stripped from the insulation layer.
CA 0223826~ l998-0~-2l Stripping the semiconductive shield layer from the insulation shield layer is often very difficult. In a situation where the semiconductive shield layer contains carbon black, a carbon ci~nt~ining residue on the surface of the insulation shield often results . The carbon residue may disadvantageously promote treeing in the insulation layer which will S Illtim~tely lead to electrical breakdown of the cable. It is therefore advantageous and desirable for a semicon~ ctive shield layer to have a low strip force (be easily separable) when being removed from the insulation layer and for the semiconductive shield layer to leave minim~l amounts of carbon residue on the surface of the in~lllAti-~n shield.
SL-;y,~Jablc conductive shield compositions are those which can be separated from a crosslinked insulation layer without leaving app~cciable amounts of residue on the insulation layer. Usually, the force re~uired to separate a strippable conductive shield composition is significantly lower than the separation force required for bonded shield compositions.
There is a significant cost difference between strippable and bonded semiconductive shield compositions based on existing technological ~ppluaches. It would be advantageous, to produce more cost effective strippable forrnulations than those developed from the teçhnic~l a~,luaches utilized to date.
Sl-mm~ry of the Invention The present invention provides a col-"~o~ilion comprising:
25-75%, by weight, based on the total weight of the composition, of an ethylene cont~inin~ polymer;
24-74%, by weight, based on the total weight of the composition, of a treated filler material; and 1-10%, by weight, based on the total weight of the composition, of a crosslinking agent;
wherein the treated filler material comprises 0.05-40%, by weight, based on the weight of the treated filler material, of a treating agent, and said treating agent is a polymer comprising acrylonitrile and at least one monomer selected from butadiene, isoprene, ethylene, propene, butene, hexene, octene, styrene, vinyl toluene, alpha methyl styrene, vinylidene chloride, vinyl chloride, acrylic acid, a Ci - Cg alkyl ester of acrylic acid, methacrylic acid, or a Cl - Cg alkyl ester of methacrylic acid; with acrylonitrile COln~l isi..g 0.5-55%, by weight, based on the weight of the treating agent.
CA 0223826~ 1998-0~-21 Wo 97/19134 PCT/US96/18481 Preferably the ethylene containing polytner is: an ethylene vinyl acetate (EVA3 polymer, ethylene propylene rubber (EPR) or ethylene propylene diene monomer (EPDM). More ~ f~ably~ the ethylene containing polymer is an EVA polymer whereinthe EVA polymer comprises 16-55%, by weight, based on the weight of the EVA polymer of a vinyl acetate monomer. A p~cr~ Gd treated filler material is a treated c&,l,ollaceous material, more preferably a treated carbon black. A preferred treating agent comprises:
acrylonitrile and butadiene. More preferably, the treating agent COl~-p- ises an acrylonitrile bnt~iiene, or a carboxylated acrylonitrile b~lf~iene polymer cont~ining 20-55%, by weight, based on the weight of the treating agent, of an acrylonitrile monomer. Preferred crosclinking agents are an organic peroxide, such as dicumyl peroxide, sulfur, or a sulfur donor system. A preferred composition of the present invention is semiconductive.
The present invention also includes an article of m~nllf~l~fllre produced ~ltili7ing the composition of the present invention. A prer~lled article of m~mlf~ctllre is cable insulation comprising a semiconductive composilion of the present invention bonded to an insulation layer, wherein the insulation layer preferably includes an ethylene homopolymer or copolymer.
An advantage of the compositions of the present invention which are semiconductive is that the semiconductive compositions may be utilized as strippable semicon-ll-ctive shield compositions in wire and cable insulation applications.
Further details and advantages of the present invention are set forth in the following more detailed description.
Detailed Description of the Invention According to the present invention, a composition comprises:
25-75%, by weight, based on the total weight of the composition, of an ethylene containing polymer;
24-74%, preferably 30-45%, by weight, based on the total weight of the composition, of a treated filler material; and 1-10%, preferably 1-6%, by weight, based on the total weight of the composition,of a crosslinking agent;
wherein the treated filler material comprises 0.05-40%, preferably 0.5-20%, morepreferably 4-15%, by weight, based on the weight of the treated filler material, of a treating agent, and said treating agent is a polymer COlll~l ising acrylonitrile and at least CA 0223826~ 1998-0~-21 one monomer selected from: b--t~ ?ne isoprene, ethylene, propene, butene, hexene, octene, styrene, vinyl toluene, alpha methyl styrene, vinylidene chloride, vinyl chloride, acrylic acid, a C~ - C8 alkyl ester of acrylic acid, methacrylic acid, or a Cl - C8 alkyl ester of methacrylic acid; with acrylonitrile comprising 0.5-55%, preferably 20-55%, more preferably 30-45%, by weight, based on the weight of the treating agent.
The ethylene c~ nt~ining polymer of the composition of the present invention is preferably: an ethylene vinyl acetate (EVA) polymer, ethylene propylene rubber ~EPR) or ethylene propylene diene monomer ~EPDM). More preferably, the ethylene c~nt~ining polymer is an EVA polymer wherein the EVA polymer ~;O~ l ises 16-55%, preferably 18-45%, by weight, based on the weight of the EVA polymer of a vinyl acetate monomer.
A preferred treated filler material is a treated carbonaceous material, more preferably a treated carbon black. A preferred treating agent comprises: acrylonitrile and butadiene. More ~ ,bly, the treating agent comprises an acrylonitrile butadiene, or carboxylated acrylonitrile bl-t~ ene polymer containing 20-55%, by weight, based on the weight of the treating agent, of an acrylonitrile monomer.
Preferred crocclinking agents are an organic peroxide, such as dicumyl peroxide,sulfur, or a sulfur donor system.
A preferred composition of the present invention is semiconductive.
The composition of the present invention may include other conventional additives such as coagents, processing additives, hydrocarbon oils, stabilizers,accelerators, antioxidants, curing agents, vinyl silane and the like. Preferably the composition is curable.
The compositions of the present invention may be produced in any manner known to the art for combining polymers and particulate components. A preferred method for producing the compositions of the present invention is compounding using a batch or continuous mixer such as a Banbury mixer, Twin Screw extruder or Buss kneader. The compositions of the present invention may be cured in manners conventional in the art.
A treated filler material compl ises a filler material and a treating agent. Suitable filler materials for use in the composition of the present invention include, but are not limited to, carbonaceous filler materials such as carbon black and graphite, and metal oxides such as silica.
CA 0223826~ 1 998 - 0~ - 21 A l~ier~ d filler material for use in the present invention is a carbonaceous material, more ~.ef~"ably carbon black. The carbon black may be any carbon black such as a furnace carbon black, a thermal carbon black, an acetylene black, and a carbon black produced by a gasification process. While any carbon black may be utilized in the S compositions of the present invention, preferably the carbon black COIllpOl~ell~ of the treated filler material has an iodine number (I2No.) of 10 to 1800 mg/g, preferably 18 to 250 mg/g, and a fluffy dibutyl phth~l~te absorption value (DBP) of 40 to 350 cc/ I OOg, pl.:r~lc.bly90to 180cctlOOg.
A ".~rel--,d treated filler material is a carbon black treated with 0.05% to 40%, preferably 0.5% to 20%, and more preferably 4% to 15%, by weight, based on the weight of the treated carbon black, of a treating agent, wherein the treating agent comprises a polymer COlll~ illg acrylonitrile and at least one monomer selected from: butadiene, isoprene, ethylene, propene, butene, hexene, octene, styrene, vinyl toluene, alpha methyl styrene, vinylidene chloride, vinyl chloride, acrylic acid, a Cl - Cg alkyl ester of acrylic acid, methacrylic acid, or a Cl - C8 alkyl ester of methacrylic acid; with acrylonitrile co~ ,; .h~g 0.5-55%, preferably 20-55%, more preferably 30-45%, by weight, based on the weight of the treating agen~. A ~,. ef~ d treating agent comprises: acrylonitrile and but~ ne. More preferably, the treating agent comprises an acrylonitrile butadiene or carboxylated acrylonitrile butadiene polymer cont~ining 20-55%, more preferably 30-45%, by weight, based on the weight of the treating agent, of an acrylonitrile monomer.
A treated filler material suitable for use in the co...po~iLions of the present invention may be produced in any manner known in the art, such as by physically blending the cu~ onw L~, melt mixing the cu~pollcnts or combining the componentswhile pelletizing the filler. The treated filler material may be produced, in dry form, by a conventional pelletizing process. For example, treated filler material for use in the compositions of the present invention may be produced by contacting a filler, e.g. a fluffy carbon black, in a pin pelletizer with an aqueous dispersion containing a treating agent to form wet pellets and then heating the wet pellets under controlled temperature and time parameters such that the water is removed from the pellets without the treating agent undergoing s~lb~ decomposition.
Pin pelletizers which may be utilized to produce a treated filler material for use in compositions of the present invention are known in the art and include the pin pelletizer described in U.S. Patent No. 3,528,785, the disclosure of which is hereby inco. ~ola~;d by CA 0223826~ 1998-0~-21 reference. U.S. Patent No. 3,528,785 also describes a conventional pelletizing process which may be utilized to produce a treated filler material for use in the compositions of the present invention.
The present invention also includes an article of m~mlf~cture produced utili7ingS the cu~ osilion of the present invention. A ~I~Ç~ d article of m~m-f~cture is an extruded article, such as a profile, tube, tape or film. Also pref~ .lcd as an article of manufacture of the present invention is a medium, or high, voltage cable comprising:
a metal conductor core;
a semiconductive shield;
an insulation layer; and an outer semicon-luctive layer, wherein a semiconductive composition of the present invention is utilized in the semiconductive shield and/or the outer semiconductive layer. The articles of m~nllf~tllre of the present invention may be produced using conventional techniques uti~ized by those of ordinary skill in the art.
The effectiveness and advantages of various aspects and embodiments of the present invention will be further illustrated by the following examples wherein the following testing procedures were utilized.
The following testing procedures were utilized in the determination and evaluation of the analytical properties of the carbon blacks utilized in the following examples. The DBP (dibutyl phthalate adsorption value) of the carbon blacks utilized in the examples, ~,essed as cubic centimeters DBP per 100 grams carbon black (cc/lOOg), was determined according to the procedure set forth in ASTM D2414. The lodine number ~I2No.) of the carbon blacks utilized in the examples, e~ e~ ed as milligrams per gram (mg/g), was determined according to ASTM test procedure D 1510.
The peel force was determined by producing a plaque of the composition Utiii~.ing a heated hydraulic press (temperature 130~ C~ to produce 1.2 millimeters ~mm) thick plaque. A 2mm thick polyethylene plaque containing 1% dicumyl peroxide was produced in a similar manner. The two plaques were l~min~t~d together under a pressure of 100 psi and exposed to a curing cycle of 180~ C for 15 minutPs The resulting laminate was allowed to cool to ambient temperature under p.~;s~ule. The strip force required to delaminate the composition layer from the polyethylene layer, at a peeling angle of 180~
and a separation speed of 3.94 inches/minute was recorded as peel force. The error of the test is typically +/-0.1 Ib/0.5 in.
CA 0223826~ 1998-0~-21 Fx~rnples Fourteen compositions, A-N, were produced utili7:ing two carbon blacks, CBI
and CB2, as filler materiat. Carbon blacks CBl and CB2 had the properties set forth in 5Table 1 below.
Table I
Iodine No. Fluffy DBP
Carbon Black ~glg cc/lOOg CB2 20 l 31 Co,--po~iLions B, C, }~, G, I, K, L, M and N were examples of compositions of the present invention and were produced lltili7ing a treated carbon black co,..~. ;si..g carbon black and HYCAR~ 1571 a car~oxylated acrylonitrile butadiene latex polymer produced and sold by BF Goodrich, Akron, Ohio.
Compositions A, D, ~, H and J were control compositions produced utilizing untreated carbon black pellets.
The treated carbon blacks utilized in co.l.po~iLions B,C, E, G, I, K, L, M and N, were produced by combining fluffy carbon black with HYCAR~ 1571 a carboxylated acl~rlonitrile butadiene latex polymer and water, to form wet pellets, in a continuous pin pelletizer. The control carbon black pellets utilized in compositions A, D, F, H and J
were produced in similar fashion except without addition of any treating agent. The resultant wet pellets were dried at a temperature which was sufficient to remove the water without causing decomposition of the polymer. In these experiments, drying c.alu.es in the range of 120~ C to 180~ C were found to be acceptable.
The compositions were produced using a Banbury mixer by compounding the carbon black pellets with ELVAX EVA resins (m~mlf~ctllred and sold by DuPont, Wilmingt~n, Deleware) to produce compositions comprising 40-42%, by weight, based on the weight of the composition, carbon black, 0.5%, by weight, based on the weight of the composition, AGERITE MA antioxidant (m~nufactl-red and sold by R.T. Vanderbilt Company Inc., Norwalk, Connecticut), 1.0%, by weight, based on the weight of thecomposition, VUL-CUP R peroxide curing agent (m~mlf~rtllred and sold by HerculesInc., Wilmingt.-n, Delaware) wi~h the rem~ind~r of the compositon being EVA resin and treating agent. The mixing t~ pelaLu,~; was m~int~ined below 150~ C to mininni premature cure of the compound.
The peel force of each composition was then deterrnined utili7ing the procedure described above. The results are provided in Table 2 below Table 2 TreatingCarbon Black ELVAX
Comp- Carbon Agent l ~ , %, E:VA Peel osition Black %, byby weight ~ Resin Force ,I.t* GradeIb/0.5in A CB 1 0 42 265 9.9 B CB I 1 42 265 7.5 C CB 1 4 42 265 6.2 D CB I 0 45 265 7.7 E CB I 1 45 265 6.8 F CB I 0 40 170 3.6 G CB I 2 40 170 2.2 H CB I 0 40 40L03 2.8 CB I 2 40 40L03 2.1 J CB2 0 40 40L03 2.9 K CB2 0.5 40 40L03 2.8 L CB2 1 40 40L03 2.8 M CB2 2 40 40L03 2.6 N CB2 4 40 40L03 2.3 I' The treat ng agent %"y weight, based on the weight of the treated carbon black.
~ The carbon biack loading %, by weight, based on the weight of the colllpo~ilion.
Treating agent= ~YCAR~ 1571 acrylonitrile butadiene polymer iatex These results show the reduced peel force of the compositions of the present invention (B, C, E, G, I, K, L, M and N) resulting from the use of the treated carbon blacks. This effect is noticeable for different levels of treating agent and in different EVA
resins.
It should be clearly understood that the forrns of the present invention herein described are illustrative only and are not inteltded to limit the scope of the invention.
Field of the Invention The present invention relates to a composition co~ illg a treated filler material, pler~,.dbly a treated call~unaceous filler material, a crosslinking agent and a ethylene cont~ining polymer. A ~ r~,llcd treated filler material co~ l;ses earbon black and ~ f~ d ethylene eont~ining polymers are ethylene-vinyl acetate (EVA), ethylene-propylene (EPR) and ethylene propylene diene monomer (EPr)M).
R~r~olln~l ofthe Jnvention The treating of earbon black with polymeric binders is disclosed in the art.
Previous patents disclose the art of incoll~uldlillg additives to produee pelletized treated filler materials, in partieular pelletized treated carbon blacks, with improved handling cllala~ .; ,Lics, for example, low dust.
The eonstruction of inc~ ted electrical conduetors, i.e., wire and cables designed for medium and high voltage applic~tionc, is known in the art. Typical constructions inelude a eore eonduetor whieh eomprises one or more strands of a eondueting metal or alloy such as copper or alllminllm; a layer of a semiconclurtive shielding compound; a layer of inclll~tion such as cr~ cclinked polyethylene or ethylene-propylene rubber and a layer of a semiconductive insulation shield compound overlaying the insulation.
The conductor shield, the insulation shield and the overlaying semicûnductive shield layer may be formed by either a two pass or by a single pass triple extrusion proeess. ~ two pass operation refers to a process whereby the conductor shield and the jncnl~tiQn layer are extruded in tandem and then crosslinked prior to extrusion of the semieonduetor insulation layer. A single pass triple extrusion process refers to a process in which the conductor shield, the insulation layer and the semiconductive shield are all extruded in a eommon extrusion head and crosclinkPd simultaneously. The single pass triple extrusion process minimi7~s production steps and hence is a plc:felltid method of m~nnf~chlre~ However, the single pass triple extrusion process generally makes the semiconductive shield layer more fully bonded to the insulation layer, than in a two pass operation.
Generally, in order to splice incul~ted electrical wires, or make terminal connections, the semiconductive shield layer should be stripped from the insulation layer.
CA 0223826~ l998-0~-2l Stripping the semiconductive shield layer from the insulation shield layer is often very difficult. In a situation where the semiconductive shield layer contains carbon black, a carbon ci~nt~ining residue on the surface of the insulation shield often results . The carbon residue may disadvantageously promote treeing in the insulation layer which will S Illtim~tely lead to electrical breakdown of the cable. It is therefore advantageous and desirable for a semicon~ ctive shield layer to have a low strip force (be easily separable) when being removed from the insulation layer and for the semiconductive shield layer to leave minim~l amounts of carbon residue on the surface of the in~lllAti-~n shield.
SL-;y,~Jablc conductive shield compositions are those which can be separated from a crosslinked insulation layer without leaving app~cciable amounts of residue on the insulation layer. Usually, the force re~uired to separate a strippable conductive shield composition is significantly lower than the separation force required for bonded shield compositions.
There is a significant cost difference between strippable and bonded semiconductive shield compositions based on existing technological ~ppluaches. It would be advantageous, to produce more cost effective strippable forrnulations than those developed from the teçhnic~l a~,luaches utilized to date.
Sl-mm~ry of the Invention The present invention provides a col-"~o~ilion comprising:
25-75%, by weight, based on the total weight of the composition, of an ethylene cont~inin~ polymer;
24-74%, by weight, based on the total weight of the composition, of a treated filler material; and 1-10%, by weight, based on the total weight of the composition, of a crosslinking agent;
wherein the treated filler material comprises 0.05-40%, by weight, based on the weight of the treated filler material, of a treating agent, and said treating agent is a polymer comprising acrylonitrile and at least one monomer selected from butadiene, isoprene, ethylene, propene, butene, hexene, octene, styrene, vinyl toluene, alpha methyl styrene, vinylidene chloride, vinyl chloride, acrylic acid, a Ci - Cg alkyl ester of acrylic acid, methacrylic acid, or a Cl - Cg alkyl ester of methacrylic acid; with acrylonitrile COln~l isi..g 0.5-55%, by weight, based on the weight of the treating agent.
CA 0223826~ 1998-0~-21 Wo 97/19134 PCT/US96/18481 Preferably the ethylene containing polytner is: an ethylene vinyl acetate (EVA3 polymer, ethylene propylene rubber (EPR) or ethylene propylene diene monomer (EPDM). More ~ f~ably~ the ethylene containing polymer is an EVA polymer whereinthe EVA polymer comprises 16-55%, by weight, based on the weight of the EVA polymer of a vinyl acetate monomer. A p~cr~ Gd treated filler material is a treated c&,l,ollaceous material, more preferably a treated carbon black. A preferred treating agent comprises:
acrylonitrile and butadiene. More preferably, the treating agent COl~-p- ises an acrylonitrile bnt~iiene, or a carboxylated acrylonitrile b~lf~iene polymer cont~ining 20-55%, by weight, based on the weight of the treating agent, of an acrylonitrile monomer. Preferred crosclinking agents are an organic peroxide, such as dicumyl peroxide, sulfur, or a sulfur donor system. A preferred composition of the present invention is semiconductive.
The present invention also includes an article of m~nllf~l~fllre produced ~ltili7ing the composition of the present invention. A prer~lled article of m~mlf~ctllre is cable insulation comprising a semiconductive composilion of the present invention bonded to an insulation layer, wherein the insulation layer preferably includes an ethylene homopolymer or copolymer.
An advantage of the compositions of the present invention which are semiconductive is that the semiconductive compositions may be utilized as strippable semicon-ll-ctive shield compositions in wire and cable insulation applications.
Further details and advantages of the present invention are set forth in the following more detailed description.
Detailed Description of the Invention According to the present invention, a composition comprises:
25-75%, by weight, based on the total weight of the composition, of an ethylene containing polymer;
24-74%, preferably 30-45%, by weight, based on the total weight of the composition, of a treated filler material; and 1-10%, preferably 1-6%, by weight, based on the total weight of the composition,of a crosslinking agent;
wherein the treated filler material comprises 0.05-40%, preferably 0.5-20%, morepreferably 4-15%, by weight, based on the weight of the treated filler material, of a treating agent, and said treating agent is a polymer COlll~l ising acrylonitrile and at least CA 0223826~ 1998-0~-21 one monomer selected from: b--t~ ?ne isoprene, ethylene, propene, butene, hexene, octene, styrene, vinyl toluene, alpha methyl styrene, vinylidene chloride, vinyl chloride, acrylic acid, a C~ - C8 alkyl ester of acrylic acid, methacrylic acid, or a Cl - C8 alkyl ester of methacrylic acid; with acrylonitrile comprising 0.5-55%, preferably 20-55%, more preferably 30-45%, by weight, based on the weight of the treating agent.
The ethylene c~ nt~ining polymer of the composition of the present invention is preferably: an ethylene vinyl acetate (EVA) polymer, ethylene propylene rubber ~EPR) or ethylene propylene diene monomer ~EPDM). More preferably, the ethylene c~nt~ining polymer is an EVA polymer wherein the EVA polymer ~;O~ l ises 16-55%, preferably 18-45%, by weight, based on the weight of the EVA polymer of a vinyl acetate monomer.
A preferred treated filler material is a treated carbonaceous material, more preferably a treated carbon black. A preferred treating agent comprises: acrylonitrile and butadiene. More ~ ,bly, the treating agent comprises an acrylonitrile butadiene, or carboxylated acrylonitrile bl-t~ ene polymer containing 20-55%, by weight, based on the weight of the treating agent, of an acrylonitrile monomer.
Preferred crocclinking agents are an organic peroxide, such as dicumyl peroxide,sulfur, or a sulfur donor system.
A preferred composition of the present invention is semiconductive.
The composition of the present invention may include other conventional additives such as coagents, processing additives, hydrocarbon oils, stabilizers,accelerators, antioxidants, curing agents, vinyl silane and the like. Preferably the composition is curable.
The compositions of the present invention may be produced in any manner known to the art for combining polymers and particulate components. A preferred method for producing the compositions of the present invention is compounding using a batch or continuous mixer such as a Banbury mixer, Twin Screw extruder or Buss kneader. The compositions of the present invention may be cured in manners conventional in the art.
A treated filler material compl ises a filler material and a treating agent. Suitable filler materials for use in the composition of the present invention include, but are not limited to, carbonaceous filler materials such as carbon black and graphite, and metal oxides such as silica.
CA 0223826~ 1 998 - 0~ - 21 A l~ier~ d filler material for use in the present invention is a carbonaceous material, more ~.ef~"ably carbon black. The carbon black may be any carbon black such as a furnace carbon black, a thermal carbon black, an acetylene black, and a carbon black produced by a gasification process. While any carbon black may be utilized in the S compositions of the present invention, preferably the carbon black COIllpOl~ell~ of the treated filler material has an iodine number (I2No.) of 10 to 1800 mg/g, preferably 18 to 250 mg/g, and a fluffy dibutyl phth~l~te absorption value (DBP) of 40 to 350 cc/ I OOg, pl.:r~lc.bly90to 180cctlOOg.
A ".~rel--,d treated filler material is a carbon black treated with 0.05% to 40%, preferably 0.5% to 20%, and more preferably 4% to 15%, by weight, based on the weight of the treated carbon black, of a treating agent, wherein the treating agent comprises a polymer COlll~ illg acrylonitrile and at least one monomer selected from: butadiene, isoprene, ethylene, propene, butene, hexene, octene, styrene, vinyl toluene, alpha methyl styrene, vinylidene chloride, vinyl chloride, acrylic acid, a Cl - Cg alkyl ester of acrylic acid, methacrylic acid, or a Cl - C8 alkyl ester of methacrylic acid; with acrylonitrile co~ ,; .h~g 0.5-55%, preferably 20-55%, more preferably 30-45%, by weight, based on the weight of the treating agen~. A ~,. ef~ d treating agent comprises: acrylonitrile and but~ ne. More preferably, the treating agent comprises an acrylonitrile butadiene or carboxylated acrylonitrile butadiene polymer cont~ining 20-55%, more preferably 30-45%, by weight, based on the weight of the treating agent, of an acrylonitrile monomer.
A treated filler material suitable for use in the co...po~iLions of the present invention may be produced in any manner known in the art, such as by physically blending the cu~ onw L~, melt mixing the cu~pollcnts or combining the componentswhile pelletizing the filler. The treated filler material may be produced, in dry form, by a conventional pelletizing process. For example, treated filler material for use in the compositions of the present invention may be produced by contacting a filler, e.g. a fluffy carbon black, in a pin pelletizer with an aqueous dispersion containing a treating agent to form wet pellets and then heating the wet pellets under controlled temperature and time parameters such that the water is removed from the pellets without the treating agent undergoing s~lb~ decomposition.
Pin pelletizers which may be utilized to produce a treated filler material for use in compositions of the present invention are known in the art and include the pin pelletizer described in U.S. Patent No. 3,528,785, the disclosure of which is hereby inco. ~ola~;d by CA 0223826~ 1998-0~-21 reference. U.S. Patent No. 3,528,785 also describes a conventional pelletizing process which may be utilized to produce a treated filler material for use in the compositions of the present invention.
The present invention also includes an article of m~mlf~cture produced utili7ingS the cu~ osilion of the present invention. A ~I~Ç~ d article of m~m-f~cture is an extruded article, such as a profile, tube, tape or film. Also pref~ .lcd as an article of manufacture of the present invention is a medium, or high, voltage cable comprising:
a metal conductor core;
a semiconductive shield;
an insulation layer; and an outer semicon-luctive layer, wherein a semiconductive composition of the present invention is utilized in the semiconductive shield and/or the outer semiconductive layer. The articles of m~nllf~tllre of the present invention may be produced using conventional techniques uti~ized by those of ordinary skill in the art.
The effectiveness and advantages of various aspects and embodiments of the present invention will be further illustrated by the following examples wherein the following testing procedures were utilized.
The following testing procedures were utilized in the determination and evaluation of the analytical properties of the carbon blacks utilized in the following examples. The DBP (dibutyl phthalate adsorption value) of the carbon blacks utilized in the examples, ~,essed as cubic centimeters DBP per 100 grams carbon black (cc/lOOg), was determined according to the procedure set forth in ASTM D2414. The lodine number ~I2No.) of the carbon blacks utilized in the examples, e~ e~ ed as milligrams per gram (mg/g), was determined according to ASTM test procedure D 1510.
The peel force was determined by producing a plaque of the composition Utiii~.ing a heated hydraulic press (temperature 130~ C~ to produce 1.2 millimeters ~mm) thick plaque. A 2mm thick polyethylene plaque containing 1% dicumyl peroxide was produced in a similar manner. The two plaques were l~min~t~d together under a pressure of 100 psi and exposed to a curing cycle of 180~ C for 15 minutPs The resulting laminate was allowed to cool to ambient temperature under p.~;s~ule. The strip force required to delaminate the composition layer from the polyethylene layer, at a peeling angle of 180~
and a separation speed of 3.94 inches/minute was recorded as peel force. The error of the test is typically +/-0.1 Ib/0.5 in.
CA 0223826~ 1998-0~-21 Fx~rnples Fourteen compositions, A-N, were produced utili7:ing two carbon blacks, CBI
and CB2, as filler materiat. Carbon blacks CBl and CB2 had the properties set forth in 5Table 1 below.
Table I
Iodine No. Fluffy DBP
Carbon Black ~glg cc/lOOg CB2 20 l 31 Co,--po~iLions B, C, }~, G, I, K, L, M and N were examples of compositions of the present invention and were produced lltili7ing a treated carbon black co,..~. ;si..g carbon black and HYCAR~ 1571 a car~oxylated acrylonitrile butadiene latex polymer produced and sold by BF Goodrich, Akron, Ohio.
Compositions A, D, ~, H and J were control compositions produced utilizing untreated carbon black pellets.
The treated carbon blacks utilized in co.l.po~iLions B,C, E, G, I, K, L, M and N, were produced by combining fluffy carbon black with HYCAR~ 1571 a carboxylated acl~rlonitrile butadiene latex polymer and water, to form wet pellets, in a continuous pin pelletizer. The control carbon black pellets utilized in compositions A, D, F, H and J
were produced in similar fashion except without addition of any treating agent. The resultant wet pellets were dried at a temperature which was sufficient to remove the water without causing decomposition of the polymer. In these experiments, drying c.alu.es in the range of 120~ C to 180~ C were found to be acceptable.
The compositions were produced using a Banbury mixer by compounding the carbon black pellets with ELVAX EVA resins (m~mlf~ctllred and sold by DuPont, Wilmingt~n, Deleware) to produce compositions comprising 40-42%, by weight, based on the weight of the composition, carbon black, 0.5%, by weight, based on the weight of the composition, AGERITE MA antioxidant (m~nufactl-red and sold by R.T. Vanderbilt Company Inc., Norwalk, Connecticut), 1.0%, by weight, based on the weight of thecomposition, VUL-CUP R peroxide curing agent (m~mlf~rtllred and sold by HerculesInc., Wilmingt.-n, Delaware) wi~h the rem~ind~r of the compositon being EVA resin and treating agent. The mixing t~ pelaLu,~; was m~int~ined below 150~ C to mininni premature cure of the compound.
The peel force of each composition was then deterrnined utili7ing the procedure described above. The results are provided in Table 2 below Table 2 TreatingCarbon Black ELVAX
Comp- Carbon Agent l ~ , %, E:VA Peel osition Black %, byby weight ~ Resin Force ,I.t* GradeIb/0.5in A CB 1 0 42 265 9.9 B CB I 1 42 265 7.5 C CB 1 4 42 265 6.2 D CB I 0 45 265 7.7 E CB I 1 45 265 6.8 F CB I 0 40 170 3.6 G CB I 2 40 170 2.2 H CB I 0 40 40L03 2.8 CB I 2 40 40L03 2.1 J CB2 0 40 40L03 2.9 K CB2 0.5 40 40L03 2.8 L CB2 1 40 40L03 2.8 M CB2 2 40 40L03 2.6 N CB2 4 40 40L03 2.3 I' The treat ng agent %"y weight, based on the weight of the treated carbon black.
~ The carbon biack loading %, by weight, based on the weight of the colllpo~ilion.
Treating agent= ~YCAR~ 1571 acrylonitrile butadiene polymer iatex These results show the reduced peel force of the compositions of the present invention (B, C, E, G, I, K, L, M and N) resulting from the use of the treated carbon blacks. This effect is noticeable for different levels of treating agent and in different EVA
resins.
It should be clearly understood that the forrns of the present invention herein described are illustrative only and are not inteltded to limit the scope of the invention.
Claims (24)
1. A polymer composition comprising:
25-75%, by weight, based on the total weight of the composition, of an ethylene containing polymer;
24-74%, by weight, based on the total weight of the composition, of a treated filler material; and 1-10%, by weight, based on the total weight of the composition, of a crosslinking agent;
wherein the treated filler material comprises 0.05-40%, by weight, based on the weight of the treated filler material, of a treating agent, and said treating agent is a polymer comprising acrylonitrile and at least one monomer selected from: butadiene, isoprene, ethylene, propene, butene, hexene, octene, styrene, vinyl toluene, alpha methyl styrene, vinylidene chloride, vinyl chloride, acrylic acid, a C1-C8 alkyl ester of acrylic acid, methacrylic acid, or a C1-C8 alkyl ester of methacrylic acid; with acrylonitrile comprising 0.5-55%, by weight, based on the weight of the treating agent.
25-75%, by weight, based on the total weight of the composition, of an ethylene containing polymer;
24-74%, by weight, based on the total weight of the composition, of a treated filler material; and 1-10%, by weight, based on the total weight of the composition, of a crosslinking agent;
wherein the treated filler material comprises 0.05-40%, by weight, based on the weight of the treated filler material, of a treating agent, and said treating agent is a polymer comprising acrylonitrile and at least one monomer selected from: butadiene, isoprene, ethylene, propene, butene, hexene, octene, styrene, vinyl toluene, alpha methyl styrene, vinylidene chloride, vinyl chloride, acrylic acid, a C1-C8 alkyl ester of acrylic acid, methacrylic acid, or a C1-C8 alkyl ester of methacrylic acid; with acrylonitrile comprising 0.5-55%, by weight, based on the weight of the treating agent.
2. The composition of claim 1 wherein the ethylene containing polymer is selected from the group consisting of: an ethylene vinyl acetate (EVA) polymer, ethylene propylene rubber (EPR) and ethylene propylene diene monomer (EPDM).
3. The composition of claim 2 wherein the ethylene containing polymer is an EVA polymer wherein the EVA polymer comprises 16-55%, by weight, based on the weight of the EVA polymer of a vinyl acetate monomer.
4. The composition of claim 1 wherein the filler material is selected from the group consisting of: carbon black, graphite and metal oxides.
5. The composition of claim 4 wherein the filler material is carbon black.
6. The composition of claim 5 wherein the treating agent is a polymer selected from: acrylonitrile-butadiene and carboxylated acrylonitrile-butadiene.
7. The composition of claim 6 wherein the acrylonitrile monomer is present in anamount of 20-55%, by weight, based on the weight of the treating agent.
8. The composition of claim 1 wherein the crosslinking agent is selected from the group consisting of: an organic peroxide, sulfur, and a sulfur donor system.
9. The composition of claim 1 wherein the composition is is semiconductive.
10. The composition of claim 1 wherein the treated filler material is present in an amount of 30-45%, by weight, based on the total weight of the composition.
11. The composition of claim 1 wherein the amount of treating agent is 0.5-20%, by weight, based on the weight of the treated filler material.
12. The composition of claim 11 wherein the amount of treating agent is 4-15%, by weight, based on the weight of the treated filler material.
13. The composition of claim 1 wherein the crosslink agent is present in an amount of 1-6%, by weight, based on the total weight of the composition.
14. The composition of claim 1 wherein the treating agent comprises 20-55%, by weight of acrylonitrile, based on the weight of the treating agent.
15. The composition of claim 1 wherein the treating agent comprises 30-45%, by weight of acrylonitrile, based on the weight of the treating agent.
16. The composition of claim 5 wherein the carbon black before treatment has an I2No. of 10-1800 mg/g.
17. The composition of claim 16 wherein the carbon black before treatment has a DBP of 40-350 cc/100g.
18. The composition of claim 1 further comprising at least one component selected from the group consisting of: a coagent, a processing additive, a hydrocarbon oil, a stabilizer, an accelerator, an antioxidant, vinyl silane and a curing agent.
19. An article of manufacture formed from the composition of claim 1.
20. An article of manufacture formed from composition of claim 3.
21. The article of manufacture of claim 19 wherein the article is a cable.
22. The article of manufacture of claim 19 wherein the article is an extruded article selected from the group consisting of: a profile, a tube, a tape and a film.
23. The article of manufacture of claim 19 wherein the composition of claim 1 isa semiconductive composition and the article of manufacture is an electric cablecomprising:
a metal conductor core;
a semiconductive shield;
an insulation layer; and an outer semiconductive layer, wherein the composition of claim 1 is utilized in at least one of: the semiconductive shield or the outer semiconductive layer.
a metal conductor core;
a semiconductive shield;
an insulation layer; and an outer semiconductive layer, wherein the composition of claim 1 is utilized in at least one of: the semiconductive shield or the outer semiconductive layer.
24. The article of manufacture of claim 23 wherein the composition of claim 1 isdirectly bonded to the insulation layer and the insulation layer comprises an ethylene homopolymer or copolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/563,283 US5747559A (en) | 1995-11-22 | 1995-11-22 | Polymeric compositions |
| US08/563,283 | 1995-11-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2238265A1 true CA2238265A1 (en) | 1997-05-29 |
Family
ID=24249884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002238265A Abandoned CA2238265A1 (en) | 1995-11-22 | 1996-11-19 | Polymeric compositions |
Country Status (18)
| Country | Link |
|---|---|
| US (2) | US5747559A (en) |
| EP (1) | EP0862597B1 (en) |
| JP (1) | JP2000500524A (en) |
| KR (1) | KR19990071566A (en) |
| CN (1) | CN1105141C (en) |
| AR (1) | AR004343A1 (en) |
| AT (1) | ATE190343T1 (en) |
| AU (1) | AU1120597A (en) |
| CA (1) | CA2238265A1 (en) |
| CO (1) | CO4560578A1 (en) |
| DE (1) | DE69607027T2 (en) |
| ES (1) | ES2144277T3 (en) |
| HK (1) | HK1015809A1 (en) |
| MY (1) | MY112999A (en) |
| NO (1) | NO316449B1 (en) |
| PE (1) | PE26097A1 (en) |
| WO (1) | WO1997019134A1 (en) |
| ZA (1) | ZA969739B (en) |
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|---|---|---|---|---|
| US6953825B1 (en) | 1995-11-22 | 2005-10-11 | Cabot Corporation | Treated carbonaceous compositions and polymer compositions containing the same |
| US6110994A (en) * | 1996-06-14 | 2000-08-29 | Cabot Corporation | Polymeric products containing modified carbon products and methods of making and using the same |
| US6472471B2 (en) | 1997-12-16 | 2002-10-29 | Cabot Corporation | Polymeric products containing modified carbon products and methods of making and using the same |
| US6336965B1 (en) * | 1998-04-03 | 2002-01-08 | Cabot Corporation | Modified pigments having improved dispersing properties |
| US6458458B1 (en) | 1998-10-13 | 2002-10-01 | Cabot Corporation | Polymer coated carbon products and other pigments and methods of making same by aqueous media polymerizations or solvent coating methods |
| CN1191308C (en) | 1999-12-02 | 2005-03-02 | 卡伯特公司 | Carbon blacks useful in wire and cable compounds |
| US6407149B1 (en) * | 1999-12-06 | 2002-06-18 | Cool Options, Inc. | Method of manufacturing an evenly colored thermally conductive composite |
| US6479571B1 (en) | 2000-01-25 | 2002-11-12 | Cabot Corporation | Elastomeric compositions containing polymer coated carbon products and other pigments |
| FR2805656B1 (en) * | 2000-02-24 | 2002-05-03 | Cit Alcatel | HIGH AND VERY HIGH VOLTAGE DIRECT CURRENT ENERGY CABLE |
| KR20010104942A (en) * | 2000-05-16 | 2001-11-28 | 이종성 | Organic Semiconducting Composition and Sensor Using the Same |
| FR2809226B1 (en) | 2000-05-19 | 2002-07-26 | Sagem | CROSSLINKABLE SEMICONDUCTOR COMPOSITION AND ELECTRICAL CABLE WITH SEMICONDUCTOR FILM |
| US6660795B2 (en) * | 2001-03-13 | 2003-12-09 | Therm-O-Disc, Incorporated | PTC conductive polymer compositions |
| US6852790B2 (en) * | 2001-04-06 | 2005-02-08 | Cabot Corporation | Conductive polymer compositions and articles containing same |
| JP5013872B2 (en) * | 2003-06-09 | 2012-08-29 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー | Peelable semiconductor insulation shield |
| CN1969763A (en) * | 2004-06-15 | 2007-05-30 | 株式会社东芝 | Acoustic backing composition, ultrasonic probe, and ultrasonic diagnostic apparatus |
| KR100645649B1 (en) * | 2004-11-03 | 2006-11-15 | 주식회사 엘지화학 | Vinyl chloride resin composition and method for preparing thereof |
| JP2009521535A (en) * | 2005-08-08 | 2009-06-04 | キャボット コーポレイション | Polymer composition comprising nanotubes |
| WO2008133888A1 (en) * | 2007-04-24 | 2008-11-06 | Cabot Corporation | Low structure carbon black and method of making same |
| WO2008153972A2 (en) * | 2007-06-08 | 2008-12-18 | Cabot Corporation | Carbon blacks, toners, and composites and methods of making same |
| JP5438332B2 (en) * | 2009-02-05 | 2014-03-12 | 昭和電線ケーブルシステム株式会社 | High voltage electronics cable |
| CN101891916A (en) * | 2010-07-06 | 2010-11-24 | 苏州市双鑫新材料科技有限公司 | Peroxide crosslinked type semi-conductive screen material for crosslinked cable conductor |
| EP2847266B1 (en) * | 2012-05-10 | 2019-03-13 | Dow Global Technologies LLC | Ethylene polymer conductor coatings prepared with polybutadiene cross-linking coagents |
| CA3001160C (en) * | 2015-10-07 | 2023-10-17 | Union Carbide Chemicals & Plastics Technology Llc | Semiconductive shield composition |
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|---|---|---|---|---|
| US3959558A (en) * | 1967-11-01 | 1976-05-25 | General Electric Company | Pressureless curing system for chemically cross-linking ethylene-containing polymers and product formed thereby |
| JPS5576508A (en) * | 1978-12-01 | 1980-06-09 | Sumitomo Electric Industries | Method of fabricating crosslinked polyethylene cable |
| JPS5662846A (en) * | 1979-10-29 | 1981-05-29 | Mitsubishi Petrochem Co Ltd | Semiconductive resin composition |
| US4451536A (en) * | 1982-06-15 | 1984-05-29 | National Distillers And Chemical Corporation | Heat distortion-resistant thermoplastic semi-conductive composition |
| GB8506304D0 (en) * | 1985-03-12 | 1985-04-11 | Bp Chem Int Ltd | Polymer composition |
| US4880857A (en) * | 1986-12-17 | 1989-11-14 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Carbon black-graft polymer, method for production thereof, and use thereof |
| DE3806548C2 (en) * | 1987-03-04 | 1996-10-02 | Toyoda Chuo Kenkyusho Kk | Composite material and process for its manufacture |
| CA2106853C (en) * | 1991-04-02 | 1997-04-08 | Bernard Aladenize | Material for semiconductor screen |
| EP0578245A3 (en) * | 1992-07-10 | 1994-07-27 | Mitsubishi Petrochemical Co | Process for producing a resin compound |
| JPH06157441A (en) * | 1992-11-30 | 1994-06-03 | Sekisui Chem Co Ltd | Photopolymerizable diacetylene compound |
| US5426136A (en) * | 1993-03-24 | 1995-06-20 | Ppg Industries, Inc. | Particulate amorphous silica associated with thin polymeric film |
| US5725650A (en) | 1995-03-20 | 1998-03-10 | Cabot Corporation | Polyethylene glycol treated carbon black and compounds thereof |
| US6953825B1 (en) | 1995-11-22 | 2005-10-11 | Cabot Corporation | Treated carbonaceous compositions and polymer compositions containing the same |
-
1995
- 1995-11-22 US US08/563,283 patent/US5747559A/en not_active Expired - Lifetime
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1996
- 1996-11-19 AU AU11205/97A patent/AU1120597A/en not_active Abandoned
- 1996-11-19 KR KR1019980703841A patent/KR19990071566A/en not_active Application Discontinuation
- 1996-11-19 DE DE69607027T patent/DE69607027T2/en not_active Expired - Lifetime
- 1996-11-19 AT AT96942019T patent/ATE190343T1/en not_active IP Right Cessation
- 1996-11-19 EP EP96942019A patent/EP0862597B1/en not_active Expired - Lifetime
- 1996-11-19 CN CN96199648A patent/CN1105141C/en not_active Expired - Lifetime
- 1996-11-19 WO PCT/US1996/018481 patent/WO1997019134A1/en not_active Application Discontinuation
- 1996-11-19 JP JP9519826A patent/JP2000500524A/en active Pending
- 1996-11-19 CA CA002238265A patent/CA2238265A1/en not_active Abandoned
- 1996-11-19 ES ES96942019T patent/ES2144277T3/en not_active Expired - Lifetime
- 1996-11-20 ZA ZA969739A patent/ZA969739B/en unknown
- 1996-11-21 MY MYPI96004857A patent/MY112999A/en unknown
- 1996-11-22 CO CO96061700A patent/CO4560578A1/en unknown
- 1996-11-22 PE PE1996000839A patent/PE26097A1/en not_active Application Discontinuation
- 1996-11-22 AR ARP960105303A patent/AR004343A1/en active IP Right Grant
-
1998
- 1998-02-17 US US09/024,796 patent/US6197848B1/en not_active Expired - Lifetime
- 1998-05-20 NO NO19982300A patent/NO316449B1/en unknown
-
1999
- 1999-03-02 HK HK99100867A patent/HK1015809A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ATE190343T1 (en) | 2000-03-15 |
| CN1105141C (en) | 2003-04-09 |
| NO982300L (en) | 1998-07-21 |
| NO316449B1 (en) | 2004-01-26 |
| HK1015809A1 (en) | 1999-10-22 |
| US6197848B1 (en) | 2001-03-06 |
| ES2144277T3 (en) | 2000-06-01 |
| DE69607027D1 (en) | 2000-04-13 |
| MY112999A (en) | 2001-10-31 |
| ZA969739B (en) | 1997-06-10 |
| CN1207754A (en) | 1999-02-10 |
| AR004343A1 (en) | 1998-11-04 |
| EP0862597A1 (en) | 1998-09-09 |
| EP0862597B1 (en) | 2000-03-08 |
| AU1120597A (en) | 1997-06-11 |
| PE26097A1 (en) | 1997-11-06 |
| WO1997019134A1 (en) | 1997-05-29 |
| KR19990071566A (en) | 1999-09-27 |
| US5747559A (en) | 1998-05-05 |
| JP2000500524A (en) | 2000-01-18 |
| DE69607027T2 (en) | 2000-09-14 |
| CO4560578A1 (en) | 1998-02-10 |
| NO982300D0 (en) | 1998-05-20 |
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