CA1115044A - Polyethylene composition containing talc filler for electrical applications - Google Patents
Polyethylene composition containing talc filler for electrical applicationsInfo
- Publication number
- CA1115044A CA1115044A CA303,203A CA303203A CA1115044A CA 1115044 A CA1115044 A CA 1115044A CA 303203 A CA303203 A CA 303203A CA 1115044 A CA1115044 A CA 1115044A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- parts
- ethylene
- ethylene polymer
- weight
- 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.)
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
Abstract
ABSTRACT OF THE DISCLOSURE
A composition for electrical applications containing ethylene polymer and talc filler coated with at least one metallic salt of a fatty acid having 8-20 carbon atoms. The composition may additionally include a flame retardant additive.
A composition for electrical applications containing ethylene polymer and talc filler coated with at least one metallic salt of a fatty acid having 8-20 carbon atoms. The composition may additionally include a flame retardant additive.
Description
3LS~
BACKGRûUND OF THE INVE~TION ~ -Field of the Invention This inve~tion r~lates to a composition for.
electrical applications based on an ethylene polymer con-taining a talc flll~r coated wLth a me~allic salt of a fatt~ acid ha~7ing 8-20 carbon a~oms.
C~mpositio~s which are employed on electrical .
wire and cable are, in many cases, prepared from c~m-positions w~ich are based on w lcanizable, or cross-li~kable, ethylene pol~mers. These ethylene pol~mer based compositions may be filled with various fillers, as well as ~
coated fillers, as described, for exampLe, i~ ~n~td Sta~es ~ ::
Pate~ts 3,148,L69, 3,832,326 a~d 3~922,422. `
. ~
~he ~iller~, when added ~o eth~lene based polymer composi~ions, reduce the cost of the c~¢position a~ well as :;
~ncrease the mechanical properties o the compositions, in that they toughen ~he ma~erials as ~or ~xample, i~creasing the abrasi~n resistance. Additio~ally, the fiI~ers decrease the flammability of the ethyle~e poIymer by their addi~lo~
thereto.
Howe~rer, there æe cer~ain ad~rerse efi~ect8 in the use of ~illed e~hyle~e poLymer based compositions. l$e :
problems encourltered in the use o fillers i~elude the fact that the insulatiorl properties, for example, arë re -~
'. '.
BACKGRûUND OF THE INVE~TION ~ -Field of the Invention This inve~tion r~lates to a composition for.
electrical applications based on an ethylene polymer con-taining a talc flll~r coated wLth a me~allic salt of a fatt~ acid ha~7ing 8-20 carbon a~oms.
C~mpositio~s which are employed on electrical .
wire and cable are, in many cases, prepared from c~m-positions w~ich are based on w lcanizable, or cross-li~kable, ethylene pol~mers. These ethylene pol~mer based compositions may be filled with various fillers, as well as ~
coated fillers, as described, for exampLe, i~ ~n~td Sta~es ~ ::
Pate~ts 3,148,L69, 3,832,326 a~d 3~922,422. `
. ~
~he ~iller~, when added ~o eth~lene based polymer composi~ions, reduce the cost of the c~¢position a~ well as :;
~ncrease the mechanical properties o the compositions, in that they toughen ~he ma~erials as ~or ~xample, i~creasing the abrasi~n resistance. Additio~ally, the fiI~ers decrease the flammability of the ethyle~e poIymer by their addi~lo~
thereto.
Howe~rer, there æe cer~ain ad~rerse efi~ect8 in the use of ~illed e~hyle~e poLymer based compositions. l$e :
problems encourltered in the use o fillers i~elude the fact that the insulatiorl properties, for example, arë re -~
'. '.
2 :
~.
11420- l susceptible to moisture, i.e., the insulation.on a finished wire or cable is more susceptible to moisture~
Additionally, the elonga~ion is generally adversely af~ected by the use of a filler. Also, i~ order to process the ethylene based compositions so as to adapt them to be placed, as,for example,~nsulation,o~ the electrical conductor components of the wire ~nd cable, it ls usuall~
., _ . .
neces~ary to a~mix the components of the compositions at high te~peratures, and ~o extrude them, again at high ~ lO temperatures, onto the electricaL conductor. When certain : filler~ are u~ed in combi~ation with certain types of ethy1ene polymers or in cert~in types of ethylene polymer based composition~, the entire curable compos~tion i8 susceptible to scorching during the high t~mparature pro-ces~ing thereof prior to the w lcanization of the composi-~ion on the electrical conductor. Scorching is, in efect, the premature w lcanization of the insulation compo~ition.
This premasure vulcanization usually occurs, when it occurs, in the barrel or die head of the extruder in which the insulation composition is being processed, at eLe~ated temperat~res, prior to its being extruded onto an elec-trical conductor, and prior to its intended vulcanizatio~.
When an insulation composition is scorched in the extruder, : the ~xtruded composition will have imperfections in the fo D of discon~inuity and roughness in the surface of the extrudate, and lumps or surface rippLes caus~d by gel particles in the body of the ex~rudate. In addition, excessive scorching may cause enough of a pre~sure build-up in the extrusion de~ice to require a ce sation of ~he extrusion operation entirel7.
Talc itsel~ is a poor filler, since the tensile and elongation properties of a t lc ~illed ethyLene pol~mer base~ c~mposi~ion are unaccep~able. Th~se unacceptable propertie~ o~ tenQile ~trength and eLongatio~ indicate ~ncompatlb~lity between the talc and ethylene poLymer.
9 ~ ~ `
L0 It ha~ now been fou~d that when aQ ethylene polymeE based c~mpo3ition which employs talc ~i~ler is coated with at ~ea8~ one metallic ~alt o~ a atty acid hav~ng 8-20 carbon at~ms, the ethylen polyme~ and talc filler are rendered c~mpatible.
An object of the present in~ention is to pro~ide ~ a ~illed;eth~lene polymer bascd composition for eLectrical : ~
; applicatio~s which has superior tensile strength, elongation . ~ :
and insul~tion resistan~e ~o mo~sture.
Another object of this in~rention is to provide scoreh resistant, curable coT~positlons based on illed .;
eth~lene polymer baqed compositi~n ha~ g such properties. ~ -A further obj ect o~ the pre~ant in~ten~ion is to pro~ide scorch resistan~ ulatio~ for electrical ~ire and c~le. ~ .
A further object of the present i~vent~ s ~o pro~ite a fla}ne resista~t composi ion for electrical in-sulation based on a i~illed e~hylene polymer composition.
' ~' ,, , ~, ,, , . , . ,:
- .. , . . .- ., , . , .. , ~
A further obj ect of the present in~Tention is to pr~vide a wire and cable conductive shield composition based on a fllled ethylene polymer containing carbon black.
These and other objects of the present in~entio~
are achieved by employing a talc iller coated wlth at least one me~alLic sal~ o~ a fatty acid havi~g 8-20 carbo~
at~ms in eth~lene polymer based compositions.
Desc~iption of the Preferred Embodiments The composition o the present lnvention comprises:
an ethylene polymer; and from about 2.5 ~o about 150 part3, preferabl.y from about 10 to about 25 parts and mo~t prefer-ably from about 25 to about 45 parts, per L00 parts o~ ethylene polymer, of talc coated with from about 0.05 to bout 5.0 parts and preferabLy ;:
from about 0.50 to a~out 2.0 p æts per hundred parts of ta}c, of at least one metallLc salt of a~long chain fatty acid o 8~20 carbon a~om~, Ano~h~r preferred embodiment of this in~e~tion is to provide a -ELame retardant composition which comprises:
an.eth~ene polymer;
~rom about 2.5 to about 150 parts, prèferably from about 10 to a~out 25 parts and most preferably about 25 to about 45 part~ per 100 parts of ~ .
: e~hylene polymer, of talc coated with rrom abou~
0.05 to about 5.0 parts and prefera~ly from abou~
'-"'~', -- ' ' , ' ,, , . -, - - .. . . . .
~ 20-1 0.50 to about 2.0 parts per hundred part~ of ~:
talc, of at least one metallic salt o~ a long chain fatty acid of 8-20 carbon atoms; and flame retardant additives in an amount su~icient to render the c~mpo8ition f~ame resistant.
The ethylene polymers which are u~ed in the com- :
po~itions of th~ pre~ent i~en~ion are solid (at 25C.) materials whlch may be homopolymers, or copolymers of ethylene. The ethylene copolymers contain at lea~t 30 weight percent of ethylene and up to about 70 weight percent of propylene, and/or up to about 50 weight percent of one or more other organic c:ompounds which are interpoLymerizable wi~h ethylene. These other compounds which are interpoly- ~
merizable with ethylene are preerabLy tho~e which contain ~ :
polymerizable un a~uration, such as is present in compounds ~o~taining an ethylene linkage, ~ C - C~ . These o~her . .
: interpolymerizable compounds may be hydrocarbon compounds . `
such as, bu~ene-l, pentene-l, isoprene, butadiene, bicyclo~
heptene, bicycloheptadiene, and styrene, as well ag vlnyL
. compounds ~uch a~ vinyl acetate and ethyL acrylate. ~:
:: :
These copoLymers couLd thus include tho~e contaln-ing ~ 0 to 70 weight percent of propylene and 30 to ~L00 ~
weig~ percen~ of ethyLene; and ~0 to~ ~ 50 weight percent ~ :
butene-l or vinyl acetate or ethyl acrylate and 50 to ~L00 :.
~ .
weight percent of ethylene; and ~ O to < 30 weight percent ::.
6.
. ,- .
~ ' . . ': - . ~
1~42~-1 of propylene, > O to 20 weight percent of butene-l and 50 to < L00 weight percent of ethylene.
The athylene polymers may be u ed indi~idually, or in combinations thereof. The ethylene polymers have a density (AS~M 1505 test procedure with conditioning as in AS~M D-1248-72) of about 0.86 to 0.96 a~d a melt index tASTM D-1238 at 44 psi test pressure)of about 0.1 to 20 decigram~ per minute.
The ethylene polymers ma~ be curable, They are cured by irradiation with high-energy electro~ beams or through the use of a chemical curing agen~.
The art of electron beam crosslinking is so highly developed that one skilled in the art is very familiar with thiq procedure.
The chemlcal curing agent is preferably an organic peroxide. The organic peroxide curing agent which can be u~ed in the present invention incLudes all organic peroxides which are capable o pro~iding free radicals or cross-linking the ethylene poLymer und~r the crosslin~ing con-ditions employed ~or the c~mpos itions.
The organic peroxide compounds can be used individually or in combination with one another.
The preferred organic peroxide compou~ds which -~
may be used in the compositions of the present in~ention may also be generally classified as those in which each 7.
~ ~.5 ~ ~ ~ 11420-1 oxygen at~ of each paro~ide group is directl7 bonded to a tertiary c~rbon atom whose remaining valance are attached to hydrocarbon radicals selected from the group con3iqting o~ alkyl, c~cloalkyl, aryl arld aralkyl, Pe~oxides of ~chi~
type are generally discLosed in U.S. 2,888,424, Examples o ~he organic perox~de compo~ds which may be used in the com~ositions o the prasent in~elltion would inc~ude^
di- ~-cumyL peroxide 2,5 dimethyl-2,5-di(t-butyl peroxy)-hex~ne-3 LO 2,5-dlm~hyl-2,5-di(t-butyl peroæy~-hexane t-butyl cum~L peroxid~
di-t-butyl peroxide .
~9 ~'-bis(t-butyL pero~y)-p-di-isopropyl benzene 2,5-dimethyl-2,5-ditbenzo~l perox~)-hexane ;;
~-bu~yl peroxy isopropyl carbonate. . ~-Addit~onally, orga~ic hydroperoxide com~ound~ as disclo~ed in U.S. Pat~nts 3,9S4,907 and 4,OL8,852 2re suitable for uC~e in ~che present iIl~ell~ioIl, The organic peroxide compou:nds are used ~n cross-Link~g ef~ective amot:mts ~n the.compositions oi~ the present i~e~t~on which may range frcm about 0.1 to 8.0, ar~d p~efer-ably abo~t 0.3 to 5.0, parts of organic peroxide compound per ~.
lOO parts by weight ~o~ ethylenè polymer in su~h- co~posi ions.
The talc filler of ~he iIlStant imJe~ iS com-mercially 2vailable in dif:feren~ ~orms and grade~. The , . .. .
D-1142~-1-C
filler ha~Y a median particle slze of fr~m 0.10 to about 10.0 microns, pre~erably frsm 0.80 to about 3.0 micron~.
Metal Salt .; ;
The metallic 8alt5 of the fat~y acld~ that can be employed herein are seleoted from the Periodic Table of the Elements, Group Ia, IIa, or IIb metal salt~j of saturat~d or unsaturated monoba~ic or dibasic, branched or 8traight chaln fatty acid~ of 8 20 csrbon atom3. Such ac~ds that may b~ ~ncluded wlthin the practice of this i~ention, bu are not lim~ted theretoy ara palmitic, stearic, lauric, oleic, sebac~c, ricinoleic and palmitoleic.
The preferred acid ic stearic acid, The preerred metal salts are calcium stearate and zlnc stearate. ;~
, Flæme Retardant -~
. : . .
~ The f1 ame-retardant additi~es useful in this in~en- ::
.
tlon compr~e a :E~ily of chem~cal compounds well known to tho~e skilled in the art. Generally speaking, the more ~ :.
lmportant of ~hese compoundR contain chemical el~ments employed for ~heir ability to impart flame resistance, e.g., .
br~mlne, chlorine, ant~mony, phosphorus and nitrogen. It is preerTed that the fl~me-retardant additive comprise a - halogenated organic compou~d (bromina~ed or chlorina~ed);
a halogen-containing organic compound ~n admlxture with an organic or inorganic antimony compound, e.g. an~imony oxlde;
elemen~al pho3phoru~ or a phosphorus compou~d; a halogen- ~ -' ' ~ 7k~ .
.
co~taining compound in a~mixture with a pho~phoru~ c ~ o~nd or compounds containing phosphorus-nitrogen bond~ or a mixture of two or more of the orego~ng. Al~o, alkaline earth metal hydxoxide~ such as calcium hydroxide and m~g~
nesium hydroxidè, and aluminum trih~drate are ~ultable flame retardant additives. In general, however, the amoun~ of addit~e will be fram 0.5 to a~ou~ 100 parts per hundred ~ parts of ethylene polymer. A preferred ran8e wi11 be from ; about 10 to about 75 part snd ~n e3pecially pre~erred ranga will be from about 35 ~o about 55 parts of addit~e pe~ 100 psrt~ of ethylene polymer. Smaller æmount~ o compounds highly concentrated in the elements responsible for lame-retardance wil~ be 3uf~icient, e.g., elemental red phosphorus wilL be preferred at 0.5 to about 10 parts per hundred parts of ethylene pol~mer while phosphorus in the fo~m of trlphenyl phosphate will be u~ed at 5 to 25 -~
parts of phosphate per hundred parts of ethylene polymer and so forth. Halogenated aromatics will be used at 5 to ab~t 45 parts and ~ynergists, e~g., irlorganic or orgaIlic anti-ny compounds ~uch as ~timony oxide, w~ll be u~ed at about 2 to about 20 parts per 100 parts of ethylene polymer.
Antioxidant _ 'rhe compositionQ of the present im7ention also a~rantageously include about 0. 01 ~o 3 . O and, preferably 0.05 to 1.0, parts of one or more suitable high temperature -:
antioxidants for the ethylene polgmer per 100 p tt~ of the ethylene polymer.
10.
These antioxidants are preerably s~erically hlndered phenols. Such compounds would include 1,3,5-trimethyl-2,4,6-tris(3,5-ditertiary butyl-4-hydroxy benzyl)benzene;
1,3,5-tris(3,$-ditertiary butyl-4-hydro~y benzyl)-~5-~riazine-2,4,6-(lH,3H,5H) trione;
~ etra~is- ~methylene-3-(3',5-di-~-butyl-4'-hyd~oxy phenyl)-propionate~ me~hane; and di(2 methyl-4-h~droxy-5-t-butyl pheny1)sulfide.
1,2-dihydro-2,2,4-trimethylquinoline.
Polymerized 2,2,4-trimethyl dihydroquinoline may ; also be used.
The antioxidants may be us ed indivi~ually, or in comb~nation with one another.
Carbon Black : The compositions of the present inventio~ also ` ~ a~vz~tageously incLude all electrically conductive carbon blac~cs, inclu~ing uxnace blac~cs, acetylene blacks, and channel blac~s:. Th~ carbon should have a particLe size of the order of about. 10 to about 60 millimicrons and a N2 surface area o about 10 to 1100 m2/g. About 1 to about 25, and p~e erably from a~out 2 to about 16 parts of the car~on black is used per 100 parts of the ethylene polymer.
: Adj w a ts ~ ~;
~In addition to the ethylene polymer, talc, and metal salt~ the coIpositions o the present in~ention may ~' .
~5~ 420-1 a~so contain other adjuvants o~ the types normally u~ed ln curable compositions for electric insulation, These other adju~ants would include curing agent~
flame retardant additives; antioxidants; carbon black; other `
fillers, blowing agents; nucleating agents for blown systems;
lubrica~ts; W stabilizers; dyes and coLorants; ~oltage ::
stabilizers; me~al deact~vator~; a~d coupling agents.
These adjuvants would be used in amounts des~gned to provide the intended ef~ect in the resulting compositio~.
- 10 The composition of the present invention may al80 ' be extended, or filled, with polymers other than the ethylene polymer which are compatible, i.e. can be physicalLy .
. blended or alloyed, with tha ethylene polymer. The result- :
ing compositions should contain at least about 30 weight percent o interpolymerized ethylene in all ~he polymers that may be present in the composition, based on the total . ~ ~
, : weight of the resulting c~mposition. The other poLymers ;: :
..
which may be used would include poL~vinyl chloride and polypropylene.
The total amount of ad~uvants used wiLl range ; from 0 to about:60 weight percent based on the totaL weight of the composition, Proce~sin~ of the ~ sitions - AlI of the components~of the present invention - are usually blended or compounded together prior to th~ir 12.
. -~ 20-l in~roduction into the extrusion device from which they are to be extruded onto an electrical conductor. The ethyLene poly~er and the other desired constituents may be blended together by any o the technlques used in the art to blend and compound thermoplastics to ho~ogeneous masses. Prior to blending the constituents together, the talc filler i8 coated with the metal salt by known teehniques. As regards blending, for ln~ance~ ~he compone~ts may be fluxed on a variety of apparatus incLuding multi-roll mills, screw mills, continuou~ ~ixers9 compoundlng extruders and ; Banbury miæers, or dissol~ed in mutual or compatible solvents.
When all the soLid components of the composition are a~ailable in the fonm of a powder, or as smalL particles, the compositions are most con~eniently prep æed by irst mak~ng a bLend of the components, say in a Banbury mixer or a continuous eætruder, a~d then mastlcating this blend on a hea~ed mill, for instance a two-roll mill, and the mill~ng continued until an intimate mlxture of the com-ponents is obtained. Alternati~ely, a master batch con-taining the ethylene polymer and the talc filLer or talc filler and carbon black a~d, if desired, some or all of the other components, may be added to the mass o~ polymer.
Where the ethylene polymer is not available in powder form the compositions may be made by introducing the polymer to the mill, masticating it until it forms a band æound roll, after which a blend o the remaining components is added 13.
-L56~
and the milling continued until an intimate mixture is obtained. The rolls are preferabLy maintained at a tempera- -ture which is within the range 80C to 135~C. and which is below the decomposition temperatures o~ the irst peroxide compound(s) if such are used. The composition, in the orm of a sheet, is removed from the mill and then brought into a form, typical~y dice-like pieces, suitable for subsequent processing.
After the various components o the compositions lQ of the present invention are uniformly admixed and blended together, they are further pro~essed, in acoordance with the process of the present lnvention, in conventional -. ~ extrusion apparatus.
; ~he compositions are then extruded onto a wire ` or cable, or other substrate. If the compositions of the present invention, are curable, they are extruded onto the wire or cable, or other substrate and w lcanized at elevated temperatures of about 7 180C and pre~erably at > 200-230C using conventional vulcanizing procedures.
The following examples are mereLy illustrative o~
the present invention and are not intended as ~.imitation on the scope thereo.
The compositions of these Examples were prepared by mixing in a suitable mixer all of the components together and then transferri~g these into a B2nbury mixer. Where the filler was precoated, the filler and coating material ,;
~ ~4.
.
11420- .
were separately blended to intimately coat the sur~ace o~
the filler. Then, the coated filler was mixed with the other components as indicated.
me formulations of the compositions are set forth in Table I.
:
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9~ 5Q~
!o r l ¦ ~ N O t~ i O CU 1~ o --~ ¦ ~ oI o ~ ~1 ~ 0 o o c~ ~i ~ .
o~ Uo~ O
~1 ¦ O I I I II :t I II O I O N ~i ~1 ~ .
(S\ O C~ 0 O
O I I I ~ I II O I O C~i ~i ~ :
O ~ 0 oO
--~ ¦ ~ ~ II N I I I I O I O ~U ~1 ~ N ~ ~ 8 --' I ' ' '' ~ ' ' ' ' ' '`' ~ --' o l ` ~ Nu~ O :, --~ I ~ . o I I ~ o N ~i rl ( J~ O N ~ 0 O
O I I I ~ I O I I I O t~ i ~1 :
~'1 o I . ~ I I I I . I I o o N ri r-- N
H ~¦ ~ N ~ co O
~1 o I I ~ I I I I I I o I o ~ i .
o ) O, I I I I I I ~ o ~
o~ ~ 0 o ' ~¦ ~ ~ ~ O O N r1 r~l ~ ~ 0 O '1:i I I I O I I O I r~ r~ O ~ .
O~ O cy U~1~0 g - X L
t-- N I I II I I I C~ r~i r l rl 11~ t~
C~ U~ N 11~ 0 0 r~ l ~
N O ~0 C O ~-i rC~ ;~ h Cl~ 0 , L/~ 0 O ~ ~ ~ 115 ''I o ' ~ ' ' ' ' ' ' ' ' ' o ~ ,~ ~ $ .
~ x d C) r~
.la td h rl al ~ Cl rl o H ~ v~ h ~J -- ~ rl ~rl ~ 'CJ
~ h ~ ~ h ~ ~ $ o~ ~ ~ J~ $
~ V ~ 3 ~ ~_~_~
.
. .
I -OZ~II
D--114 20--l -C
.:
The compo~t~ons in Tabla I were proce~ed into ;~
test 8pecimen8 a~ required by the follo~ing test procedures and ~ub~ected to the following test procedure~: ;
Tensile stren~th and elong~
. .
AS~M - D412-68 Insulation resis~anee Underwriter~ Laboratory Sub~ect 44 (No~ember 24, 196S) ~ , Scorch Time A con~tant we~ght of material i~ added to a .
Brabender*mixer maintained at lSOC and 50RPM and suitably adapted 80 that a torque measur~ment can be contlnuou~ly measured on the material When the material reaches 135C:, torqua mea~ure~
ment beg~n~ as measured by a Brabender Plastograph Recorder. --Torque c~ntinues to decrease until a ~gnlficant degree of ro~s-linking is occurr~g at which time torque measure-ment begin~ increasing. At the time that the torque curve intersects the zero point, scorch ls considered to have occurred. The width of a bowl shaped cuxve described by the Pla~tograph ~corder i~ the scorch time measureme~t.
Ihe wider the bowl of thi~ curve, the le.~`~ is the scorching.
~ The results of ~hese te~ts are set for~h ln ,~ :
Table II.
* Trademark 17.
,r ..
~5~ ~
o ~ o u~ o o o u-~ o n O
~ U~ o U~ ~1 o o~
o C~
.. U~ ~:
. ~C
. .. ..... .....
~ ~ ,~, ,~, 2 '' '' ~ ~g '. ' ~C ~ .
ô ~ C~
C~ 4 C~
u~ ~ a~ ~ ~ u~ . ,, . 3 ~ O
. t~ o o I C~ ~o o ~ ~ I I ~ O O O O ^
.~ H ~ ~
~ b~
~ ~c ~ ~ I o~ O~O I ~' .1 ~ ~ ~I ~ ~ 00 0 ~ O ~ ~ ~ ~ ~ :
~, ~ 3 ,~
.. ~~ I t I ' ~1 o o o o ;~ o ~ ~ ~, ~1 a~ ~ c~l ~ o ,, ~ u~
.. ~ ~1 .
~:: Q u~ o u~ o o u~ o ~ u~ In o u~ ~ O
, ~ U~ ~ O ~ 00 C~l O ~ ~ O r g U
.~ ~
a~ ~ o o o o o o o o o o Q O O O O O O
~ ~ : : :
: :
~ 8 I oz~ll These results indicate that the use of a talc filler coated with a metallic salt of the presen~ inven-tion (Examples 2 and 3~ provides a superior combination of tensile s~rength, elongation, insulation resista~ce, fLame and processing characteristics (~corch time) that are not attainable with o~her m1neral fillers and the treated mineral ~illers,particularly the silane treated ~iller~ of ~he prior art.
~ .
The compositions of these Exampleq were prepared by the methods as in ths previous Examples. me formula-; tions of these compositions are set forth in Table III.
T~BLE~
9 20 - ~
Eth71-Vinyl Acetate 59.2 59.2 54.0 ~ :
Copolymer (a) Talc 12.4 L
Clay - 12.4 Silica - - L7.2 Zinc Stearate 0.5 Siloxane (b) 0.5 Silane (c) - - O.4 Flame retardant(d) L7.3 17.3 17.2 Antimony trioxide 8.0 8.0 . 8.5 .
Antioxidant(e) 0.5 0.5 0.5 ~
Peroxide(f) 2.1 2.1 _ _2.2 ~ :
.
(a) 9-11.5% vinyl ace~ate; Melt Index 3.0;
(b) octamethylcycLotetrasiloxane;
(c) vinyl-tri-(beta-methoxyethoxy)silane;
(d) high mel~ing hydrocarbon ma~erial containing 55% chlorine manufac~ured by ~ooker Chemical Co.;
: (e) 1, 2-dihydro-2,2,4 trimethylquinoline;
(f~ di-~cumyl peroxide _indicates the filler was precoated.
19 .
-- - -~ ~ L1420 1 The compositions in Table III were proce~sed into test specimen as required by the following test procedures and subjected to the following test procedures: Tensile streng~h and elongation, ASTM-4L2-68; Modulus, ASTM-D882~
758; Qxygen Index, ASTM D-2863-70.
The results o thPse tests are set forth in Table IV.
Tensile Modulus O~ygen 10Exam~le Strength(psi) Elongation~Index 18 2180 440 L5,000 28.5 19 1570 310 12,200 26.8 20 1690 395 14,200 27.5 These results indicate that the use of a talc filler coated with a metal salt of the prasent i~vention (Example 18) pro~ides a superior combination of tensile .
strength, elo~gation,~moduLus and oxygen index that are no~
attainable with other coated mineral fillers.
.. ZO.
The composition of this Example was prepared by the methods as in the previous ExampLes. The formulation of t~is composition is as follows:
Ethylene-Ethyl Acrylate Copolymer (a) 74.8 Talc 15 01 ::
Car~on black Cb) 10.0 ~ ;
Antioxidant Cc~
: ' ~a~ 13-16% ethyl acrylate; Melt Index 1.0-2.0 ~) Electrically conductive; surface area 1000 m2/g 1 indicates that the iller was precoated The composition was extruded onto tape using a - conventional type extruding machine and subjec~ed to ~he following test procedures:
Tensile strength and elongation; and tensile strength ~
and elongation after aging in an oven for 7 days at :
100C, ASTM-412-68; Brittleness temperature, F50, ASTM D-746:; Volume resistivity at 23 and 90C, ASTM D-746.
The results of these tests are as follows:
Tensile strength ~si~ :
as molded 1730 - after heat aging 1690 Elongation (%) as molded 510 after heat aging 400 Brittleness temperature, F50 -40C.
Volume resisti~ity Cohm-cm~
90C ~ ; 5700 :' :
. .
11,420~1 Obviously, o~er modifications and variations of the present invention are possible in light of the above teac~ings. It is, therefore, to be understood that changes may be made in the particular embodiments of thls invention described which are within the full intended scope of the invention as defined by the appended claims.
, '.
.
~.
11420- l susceptible to moisture, i.e., the insulation.on a finished wire or cable is more susceptible to moisture~
Additionally, the elonga~ion is generally adversely af~ected by the use of a filler. Also, i~ order to process the ethylene based compositions so as to adapt them to be placed, as,for example,~nsulation,o~ the electrical conductor components of the wire ~nd cable, it ls usuall~
., _ . .
neces~ary to a~mix the components of the compositions at high te~peratures, and ~o extrude them, again at high ~ lO temperatures, onto the electricaL conductor. When certain : filler~ are u~ed in combi~ation with certain types of ethy1ene polymers or in cert~in types of ethylene polymer based composition~, the entire curable compos~tion i8 susceptible to scorching during the high t~mparature pro-ces~ing thereof prior to the w lcanization of the composi-~ion on the electrical conductor. Scorching is, in efect, the premature w lcanization of the insulation compo~ition.
This premasure vulcanization usually occurs, when it occurs, in the barrel or die head of the extruder in which the insulation composition is being processed, at eLe~ated temperat~res, prior to its being extruded onto an elec-trical conductor, and prior to its intended vulcanizatio~.
When an insulation composition is scorched in the extruder, : the ~xtruded composition will have imperfections in the fo D of discon~inuity and roughness in the surface of the extrudate, and lumps or surface rippLes caus~d by gel particles in the body of the ex~rudate. In addition, excessive scorching may cause enough of a pre~sure build-up in the extrusion de~ice to require a ce sation of ~he extrusion operation entirel7.
Talc itsel~ is a poor filler, since the tensile and elongation properties of a t lc ~illed ethyLene pol~mer base~ c~mposi~ion are unaccep~able. Th~se unacceptable propertie~ o~ tenQile ~trength and eLongatio~ indicate ~ncompatlb~lity between the talc and ethylene poLymer.
9 ~ ~ `
L0 It ha~ now been fou~d that when aQ ethylene polymeE based c~mpo3ition which employs talc ~i~ler is coated with at ~ea8~ one metallic ~alt o~ a atty acid hav~ng 8-20 carbon at~ms, the ethylen polyme~ and talc filler are rendered c~mpatible.
An object of the present in~ention is to pro~ide ~ a ~illed;eth~lene polymer bascd composition for eLectrical : ~
; applicatio~s which has superior tensile strength, elongation . ~ :
and insul~tion resistan~e ~o mo~sture.
Another object of this in~rention is to provide scoreh resistant, curable coT~positlons based on illed .;
eth~lene polymer baqed compositi~n ha~ g such properties. ~ -A further obj ect o~ the pre~ant in~ten~ion is to pro~ide scorch resistan~ ulatio~ for electrical ~ire and c~le. ~ .
A further object of the present i~vent~ s ~o pro~ite a fla}ne resista~t composi ion for electrical in-sulation based on a i~illed e~hylene polymer composition.
' ~' ,, , ~, ,, , . , . ,:
- .. , . . .- ., , . , .. , ~
A further obj ect of the present in~Tention is to pr~vide a wire and cable conductive shield composition based on a fllled ethylene polymer containing carbon black.
These and other objects of the present in~entio~
are achieved by employing a talc iller coated wlth at least one me~alLic sal~ o~ a fatty acid havi~g 8-20 carbo~
at~ms in eth~lene polymer based compositions.
Desc~iption of the Preferred Embodiments The composition o the present lnvention comprises:
an ethylene polymer; and from about 2.5 ~o about 150 part3, preferabl.y from about 10 to about 25 parts and mo~t prefer-ably from about 25 to about 45 parts, per L00 parts o~ ethylene polymer, of talc coated with from about 0.05 to bout 5.0 parts and preferabLy ;:
from about 0.50 to a~out 2.0 p æts per hundred parts of ta}c, of at least one metallLc salt of a~long chain fatty acid o 8~20 carbon a~om~, Ano~h~r preferred embodiment of this in~e~tion is to provide a -ELame retardant composition which comprises:
an.eth~ene polymer;
~rom about 2.5 to about 150 parts, prèferably from about 10 to a~out 25 parts and most preferably about 25 to about 45 part~ per 100 parts of ~ .
: e~hylene polymer, of talc coated with rrom abou~
0.05 to about 5.0 parts and prefera~ly from abou~
'-"'~', -- ' ' , ' ,, , . -, - - .. . . . .
~ 20-1 0.50 to about 2.0 parts per hundred part~ of ~:
talc, of at least one metallic salt o~ a long chain fatty acid of 8-20 carbon atoms; and flame retardant additives in an amount su~icient to render the c~mpo8ition f~ame resistant.
The ethylene polymers which are u~ed in the com- :
po~itions of th~ pre~ent i~en~ion are solid (at 25C.) materials whlch may be homopolymers, or copolymers of ethylene. The ethylene copolymers contain at lea~t 30 weight percent of ethylene and up to about 70 weight percent of propylene, and/or up to about 50 weight percent of one or more other organic c:ompounds which are interpoLymerizable wi~h ethylene. These other compounds which are interpoly- ~
merizable with ethylene are preerabLy tho~e which contain ~ :
polymerizable un a~uration, such as is present in compounds ~o~taining an ethylene linkage, ~ C - C~ . These o~her . .
: interpolymerizable compounds may be hydrocarbon compounds . `
such as, bu~ene-l, pentene-l, isoprene, butadiene, bicyclo~
heptene, bicycloheptadiene, and styrene, as well ag vlnyL
. compounds ~uch a~ vinyl acetate and ethyL acrylate. ~:
:: :
These copoLymers couLd thus include tho~e contaln-ing ~ 0 to 70 weight percent of propylene and 30 to ~L00 ~
weig~ percen~ of ethyLene; and ~0 to~ ~ 50 weight percent ~ :
butene-l or vinyl acetate or ethyl acrylate and 50 to ~L00 :.
~ .
weight percent of ethylene; and ~ O to < 30 weight percent ::.
6.
. ,- .
~ ' . . ': - . ~
1~42~-1 of propylene, > O to 20 weight percent of butene-l and 50 to < L00 weight percent of ethylene.
The athylene polymers may be u ed indi~idually, or in combinations thereof. The ethylene polymers have a density (AS~M 1505 test procedure with conditioning as in AS~M D-1248-72) of about 0.86 to 0.96 a~d a melt index tASTM D-1238 at 44 psi test pressure)of about 0.1 to 20 decigram~ per minute.
The ethylene polymers ma~ be curable, They are cured by irradiation with high-energy electro~ beams or through the use of a chemical curing agen~.
The art of electron beam crosslinking is so highly developed that one skilled in the art is very familiar with thiq procedure.
The chemlcal curing agent is preferably an organic peroxide. The organic peroxide curing agent which can be u~ed in the present invention incLudes all organic peroxides which are capable o pro~iding free radicals or cross-linking the ethylene poLymer und~r the crosslin~ing con-ditions employed ~or the c~mpos itions.
The organic peroxide compounds can be used individually or in combination with one another.
The preferred organic peroxide compou~ds which -~
may be used in the compositions of the present in~ention may also be generally classified as those in which each 7.
~ ~.5 ~ ~ ~ 11420-1 oxygen at~ of each paro~ide group is directl7 bonded to a tertiary c~rbon atom whose remaining valance are attached to hydrocarbon radicals selected from the group con3iqting o~ alkyl, c~cloalkyl, aryl arld aralkyl, Pe~oxides of ~chi~
type are generally discLosed in U.S. 2,888,424, Examples o ~he organic perox~de compo~ds which may be used in the com~ositions o the prasent in~elltion would inc~ude^
di- ~-cumyL peroxide 2,5 dimethyl-2,5-di(t-butyl peroxy)-hex~ne-3 LO 2,5-dlm~hyl-2,5-di(t-butyl peroæy~-hexane t-butyl cum~L peroxid~
di-t-butyl peroxide .
~9 ~'-bis(t-butyL pero~y)-p-di-isopropyl benzene 2,5-dimethyl-2,5-ditbenzo~l perox~)-hexane ;;
~-bu~yl peroxy isopropyl carbonate. . ~-Addit~onally, orga~ic hydroperoxide com~ound~ as disclo~ed in U.S. Pat~nts 3,9S4,907 and 4,OL8,852 2re suitable for uC~e in ~che present iIl~ell~ioIl, The organic peroxide compou:nds are used ~n cross-Link~g ef~ective amot:mts ~n the.compositions oi~ the present i~e~t~on which may range frcm about 0.1 to 8.0, ar~d p~efer-ably abo~t 0.3 to 5.0, parts of organic peroxide compound per ~.
lOO parts by weight ~o~ ethylenè polymer in su~h- co~posi ions.
The talc filler of ~he iIlStant imJe~ iS com-mercially 2vailable in dif:feren~ ~orms and grade~. The , . .. .
D-1142~-1-C
filler ha~Y a median particle slze of fr~m 0.10 to about 10.0 microns, pre~erably frsm 0.80 to about 3.0 micron~.
Metal Salt .; ;
The metallic 8alt5 of the fat~y acld~ that can be employed herein are seleoted from the Periodic Table of the Elements, Group Ia, IIa, or IIb metal salt~j of saturat~d or unsaturated monoba~ic or dibasic, branched or 8traight chaln fatty acid~ of 8 20 csrbon atom3. Such ac~ds that may b~ ~ncluded wlthin the practice of this i~ention, bu are not lim~ted theretoy ara palmitic, stearic, lauric, oleic, sebac~c, ricinoleic and palmitoleic.
The preferred acid ic stearic acid, The preerred metal salts are calcium stearate and zlnc stearate. ;~
, Flæme Retardant -~
. : . .
~ The f1 ame-retardant additi~es useful in this in~en- ::
.
tlon compr~e a :E~ily of chem~cal compounds well known to tho~e skilled in the art. Generally speaking, the more ~ :.
lmportant of ~hese compoundR contain chemical el~ments employed for ~heir ability to impart flame resistance, e.g., .
br~mlne, chlorine, ant~mony, phosphorus and nitrogen. It is preerTed that the fl~me-retardant additive comprise a - halogenated organic compou~d (bromina~ed or chlorina~ed);
a halogen-containing organic compound ~n admlxture with an organic or inorganic antimony compound, e.g. an~imony oxlde;
elemen~al pho3phoru~ or a phosphorus compou~d; a halogen- ~ -' ' ~ 7k~ .
.
co~taining compound in a~mixture with a pho~phoru~ c ~ o~nd or compounds containing phosphorus-nitrogen bond~ or a mixture of two or more of the orego~ng. Al~o, alkaline earth metal hydxoxide~ such as calcium hydroxide and m~g~
nesium hydroxidè, and aluminum trih~drate are ~ultable flame retardant additives. In general, however, the amoun~ of addit~e will be fram 0.5 to a~ou~ 100 parts per hundred ~ parts of ethylene polymer. A preferred ran8e wi11 be from ; about 10 to about 75 part snd ~n e3pecially pre~erred ranga will be from about 35 ~o about 55 parts of addit~e pe~ 100 psrt~ of ethylene polymer. Smaller æmount~ o compounds highly concentrated in the elements responsible for lame-retardance wil~ be 3uf~icient, e.g., elemental red phosphorus wilL be preferred at 0.5 to about 10 parts per hundred parts of ethylene pol~mer while phosphorus in the fo~m of trlphenyl phosphate will be u~ed at 5 to 25 -~
parts of phosphate per hundred parts of ethylene polymer and so forth. Halogenated aromatics will be used at 5 to ab~t 45 parts and ~ynergists, e~g., irlorganic or orgaIlic anti-ny compounds ~uch as ~timony oxide, w~ll be u~ed at about 2 to about 20 parts per 100 parts of ethylene polymer.
Antioxidant _ 'rhe compositionQ of the present im7ention also a~rantageously include about 0. 01 ~o 3 . O and, preferably 0.05 to 1.0, parts of one or more suitable high temperature -:
antioxidants for the ethylene polgmer per 100 p tt~ of the ethylene polymer.
10.
These antioxidants are preerably s~erically hlndered phenols. Such compounds would include 1,3,5-trimethyl-2,4,6-tris(3,5-ditertiary butyl-4-hydroxy benzyl)benzene;
1,3,5-tris(3,$-ditertiary butyl-4-hydro~y benzyl)-~5-~riazine-2,4,6-(lH,3H,5H) trione;
~ etra~is- ~methylene-3-(3',5-di-~-butyl-4'-hyd~oxy phenyl)-propionate~ me~hane; and di(2 methyl-4-h~droxy-5-t-butyl pheny1)sulfide.
1,2-dihydro-2,2,4-trimethylquinoline.
Polymerized 2,2,4-trimethyl dihydroquinoline may ; also be used.
The antioxidants may be us ed indivi~ually, or in comb~nation with one another.
Carbon Black : The compositions of the present inventio~ also ` ~ a~vz~tageously incLude all electrically conductive carbon blac~cs, inclu~ing uxnace blac~cs, acetylene blacks, and channel blac~s:. Th~ carbon should have a particLe size of the order of about. 10 to about 60 millimicrons and a N2 surface area o about 10 to 1100 m2/g. About 1 to about 25, and p~e erably from a~out 2 to about 16 parts of the car~on black is used per 100 parts of the ethylene polymer.
: Adj w a ts ~ ~;
~In addition to the ethylene polymer, talc, and metal salt~ the coIpositions o the present in~ention may ~' .
~5~ 420-1 a~so contain other adjuvants o~ the types normally u~ed ln curable compositions for electric insulation, These other adju~ants would include curing agent~
flame retardant additives; antioxidants; carbon black; other `
fillers, blowing agents; nucleating agents for blown systems;
lubrica~ts; W stabilizers; dyes and coLorants; ~oltage ::
stabilizers; me~al deact~vator~; a~d coupling agents.
These adjuvants would be used in amounts des~gned to provide the intended ef~ect in the resulting compositio~.
- 10 The composition of the present invention may al80 ' be extended, or filled, with polymers other than the ethylene polymer which are compatible, i.e. can be physicalLy .
. blended or alloyed, with tha ethylene polymer. The result- :
ing compositions should contain at least about 30 weight percent o interpolymerized ethylene in all ~he polymers that may be present in the composition, based on the total . ~ ~
, : weight of the resulting c~mposition. The other poLymers ;: :
..
which may be used would include poL~vinyl chloride and polypropylene.
The total amount of ad~uvants used wiLl range ; from 0 to about:60 weight percent based on the totaL weight of the composition, Proce~sin~ of the ~ sitions - AlI of the components~of the present invention - are usually blended or compounded together prior to th~ir 12.
. -~ 20-l in~roduction into the extrusion device from which they are to be extruded onto an electrical conductor. The ethyLene poly~er and the other desired constituents may be blended together by any o the technlques used in the art to blend and compound thermoplastics to ho~ogeneous masses. Prior to blending the constituents together, the talc filler i8 coated with the metal salt by known teehniques. As regards blending, for ln~ance~ ~he compone~ts may be fluxed on a variety of apparatus incLuding multi-roll mills, screw mills, continuou~ ~ixers9 compoundlng extruders and ; Banbury miæers, or dissol~ed in mutual or compatible solvents.
When all the soLid components of the composition are a~ailable in the fonm of a powder, or as smalL particles, the compositions are most con~eniently prep æed by irst mak~ng a bLend of the components, say in a Banbury mixer or a continuous eætruder, a~d then mastlcating this blend on a hea~ed mill, for instance a two-roll mill, and the mill~ng continued until an intimate mlxture of the com-ponents is obtained. Alternati~ely, a master batch con-taining the ethylene polymer and the talc filLer or talc filler and carbon black a~d, if desired, some or all of the other components, may be added to the mass o~ polymer.
Where the ethylene polymer is not available in powder form the compositions may be made by introducing the polymer to the mill, masticating it until it forms a band æound roll, after which a blend o the remaining components is added 13.
-L56~
and the milling continued until an intimate mixture is obtained. The rolls are preferabLy maintained at a tempera- -ture which is within the range 80C to 135~C. and which is below the decomposition temperatures o~ the irst peroxide compound(s) if such are used. The composition, in the orm of a sheet, is removed from the mill and then brought into a form, typical~y dice-like pieces, suitable for subsequent processing.
After the various components o the compositions lQ of the present invention are uniformly admixed and blended together, they are further pro~essed, in acoordance with the process of the present lnvention, in conventional -. ~ extrusion apparatus.
; ~he compositions are then extruded onto a wire ` or cable, or other substrate. If the compositions of the present invention, are curable, they are extruded onto the wire or cable, or other substrate and w lcanized at elevated temperatures of about 7 180C and pre~erably at > 200-230C using conventional vulcanizing procedures.
The following examples are mereLy illustrative o~
the present invention and are not intended as ~.imitation on the scope thereo.
The compositions of these Examples were prepared by mixing in a suitable mixer all of the components together and then transferri~g these into a B2nbury mixer. Where the filler was precoated, the filler and coating material ,;
~ ~4.
.
11420- .
were separately blended to intimately coat the sur~ace o~
the filler. Then, the coated filler was mixed with the other components as indicated.
me formulations of the compositions are set forth in Table I.
:
"
' '''-' .
:' .. ~ , .. ~ . . .
9~ 5Q~
!o r l ¦ ~ N O t~ i O CU 1~ o --~ ¦ ~ oI o ~ ~1 ~ 0 o o c~ ~i ~ .
o~ Uo~ O
~1 ¦ O I I I II :t I II O I O N ~i ~1 ~ .
(S\ O C~ 0 O
O I I I ~ I II O I O C~i ~i ~ :
O ~ 0 oO
--~ ¦ ~ ~ II N I I I I O I O ~U ~1 ~ N ~ ~ 8 --' I ' ' '' ~ ' ' ' ' ' '`' ~ --' o l ` ~ Nu~ O :, --~ I ~ . o I I ~ o N ~i rl ( J~ O N ~ 0 O
O I I I ~ I O I I I O t~ i ~1 :
~'1 o I . ~ I I I I . I I o o N ri r-- N
H ~¦ ~ N ~ co O
~1 o I I ~ I I I I I I o I o ~ i .
o ) O, I I I I I I ~ o ~
o~ ~ 0 o ' ~¦ ~ ~ ~ O O N r1 r~l ~ ~ 0 O '1:i I I I O I I O I r~ r~ O ~ .
O~ O cy U~1~0 g - X L
t-- N I I II I I I C~ r~i r l rl 11~ t~
C~ U~ N 11~ 0 0 r~ l ~
N O ~0 C O ~-i rC~ ;~ h Cl~ 0 , L/~ 0 O ~ ~ ~ 115 ''I o ' ~ ' ' ' ' ' ' ' ' ' o ~ ,~ ~ $ .
~ x d C) r~
.la td h rl al ~ Cl rl o H ~ v~ h ~J -- ~ rl ~rl ~ 'CJ
~ h ~ ~ h ~ ~ $ o~ ~ ~ J~ $
~ V ~ 3 ~ ~_~_~
.
. .
I -OZ~II
D--114 20--l -C
.:
The compo~t~ons in Tabla I were proce~ed into ;~
test 8pecimen8 a~ required by the follo~ing test procedures and ~ub~ected to the following test procedure~: ;
Tensile stren~th and elong~
. .
AS~M - D412-68 Insulation resis~anee Underwriter~ Laboratory Sub~ect 44 (No~ember 24, 196S) ~ , Scorch Time A con~tant we~ght of material i~ added to a .
Brabender*mixer maintained at lSOC and 50RPM and suitably adapted 80 that a torque measur~ment can be contlnuou~ly measured on the material When the material reaches 135C:, torqua mea~ure~
ment beg~n~ as measured by a Brabender Plastograph Recorder. --Torque c~ntinues to decrease until a ~gnlficant degree of ro~s-linking is occurr~g at which time torque measure-ment begin~ increasing. At the time that the torque curve intersects the zero point, scorch ls considered to have occurred. The width of a bowl shaped cuxve described by the Pla~tograph ~corder i~ the scorch time measureme~t.
Ihe wider the bowl of thi~ curve, the le.~`~ is the scorching.
~ The results of ~hese te~ts are set for~h ln ,~ :
Table II.
* Trademark 17.
,r ..
~5~ ~
o ~ o u~ o o o u-~ o n O
~ U~ o U~ ~1 o o~
o C~
.. U~ ~:
. ~C
. .. ..... .....
~ ~ ,~, ,~, 2 '' '' ~ ~g '. ' ~C ~ .
ô ~ C~
C~ 4 C~
u~ ~ a~ ~ ~ u~ . ,, . 3 ~ O
. t~ o o I C~ ~o o ~ ~ I I ~ O O O O ^
.~ H ~ ~
~ b~
~ ~c ~ ~ I o~ O~O I ~' .1 ~ ~ ~I ~ ~ 00 0 ~ O ~ ~ ~ ~ ~ :
~, ~ 3 ,~
.. ~~ I t I ' ~1 o o o o ;~ o ~ ~ ~, ~1 a~ ~ c~l ~ o ,, ~ u~
.. ~ ~1 .
~:: Q u~ o u~ o o u~ o ~ u~ In o u~ ~ O
, ~ U~ ~ O ~ 00 C~l O ~ ~ O r g U
.~ ~
a~ ~ o o o o o o o o o o Q O O O O O O
~ ~ : : :
: :
~ 8 I oz~ll These results indicate that the use of a talc filler coated with a metallic salt of the presen~ inven-tion (Examples 2 and 3~ provides a superior combination of tensile s~rength, elongation, insulation resista~ce, fLame and processing characteristics (~corch time) that are not attainable with o~her m1neral fillers and the treated mineral ~illers,particularly the silane treated ~iller~ of ~he prior art.
~ .
The compositions of these Exampleq were prepared by the methods as in ths previous Examples. me formula-; tions of these compositions are set forth in Table III.
T~BLE~
9 20 - ~
Eth71-Vinyl Acetate 59.2 59.2 54.0 ~ :
Copolymer (a) Talc 12.4 L
Clay - 12.4 Silica - - L7.2 Zinc Stearate 0.5 Siloxane (b) 0.5 Silane (c) - - O.4 Flame retardant(d) L7.3 17.3 17.2 Antimony trioxide 8.0 8.0 . 8.5 .
Antioxidant(e) 0.5 0.5 0.5 ~
Peroxide(f) 2.1 2.1 _ _2.2 ~ :
.
(a) 9-11.5% vinyl ace~ate; Melt Index 3.0;
(b) octamethylcycLotetrasiloxane;
(c) vinyl-tri-(beta-methoxyethoxy)silane;
(d) high mel~ing hydrocarbon ma~erial containing 55% chlorine manufac~ured by ~ooker Chemical Co.;
: (e) 1, 2-dihydro-2,2,4 trimethylquinoline;
(f~ di-~cumyl peroxide _indicates the filler was precoated.
19 .
-- - -~ ~ L1420 1 The compositions in Table III were proce~sed into test specimen as required by the following test procedures and subjected to the following test procedures: Tensile streng~h and elongation, ASTM-4L2-68; Modulus, ASTM-D882~
758; Qxygen Index, ASTM D-2863-70.
The results o thPse tests are set forth in Table IV.
Tensile Modulus O~ygen 10Exam~le Strength(psi) Elongation~Index 18 2180 440 L5,000 28.5 19 1570 310 12,200 26.8 20 1690 395 14,200 27.5 These results indicate that the use of a talc filler coated with a metal salt of the prasent i~vention (Example 18) pro~ides a superior combination of tensile .
strength, elo~gation,~moduLus and oxygen index that are no~
attainable with other coated mineral fillers.
.. ZO.
The composition of this Example was prepared by the methods as in the previous ExampLes. The formulation of t~is composition is as follows:
Ethylene-Ethyl Acrylate Copolymer (a) 74.8 Talc 15 01 ::
Car~on black Cb) 10.0 ~ ;
Antioxidant Cc~
: ' ~a~ 13-16% ethyl acrylate; Melt Index 1.0-2.0 ~) Electrically conductive; surface area 1000 m2/g 1 indicates that the iller was precoated The composition was extruded onto tape using a - conventional type extruding machine and subjec~ed to ~he following test procedures:
Tensile strength and elongation; and tensile strength ~
and elongation after aging in an oven for 7 days at :
100C, ASTM-412-68; Brittleness temperature, F50, ASTM D-746:; Volume resistivity at 23 and 90C, ASTM D-746.
The results of these tests are as follows:
Tensile strength ~si~ :
as molded 1730 - after heat aging 1690 Elongation (%) as molded 510 after heat aging 400 Brittleness temperature, F50 -40C.
Volume resisti~ity Cohm-cm~
90C ~ ; 5700 :' :
. .
11,420~1 Obviously, o~er modifications and variations of the present invention are possible in light of the above teac~ings. It is, therefore, to be understood that changes may be made in the particular embodiments of thls invention described which are within the full intended scope of the invention as defined by the appended claims.
, '.
.
Claims (23)
1. A composition useful for coating wires or cables, consisting essentially of:
(a) ethylene polymer, and (b) about 2.5 to about 150 parts by weight, per 100 parts by weight of ethylene polymer, of talc filler coated with at least one metallic salt of a fatty acid having 8 to 20 carbon atoms, wherein said metallic salt contains a metal selected from the metals of Groups Ia, IIa, IIb of the Mendeleev Periodic Table of Elements.
(a) ethylene polymer, and (b) about 2.5 to about 150 parts by weight, per 100 parts by weight of ethylene polymer, of talc filler coated with at least one metallic salt of a fatty acid having 8 to 20 carbon atoms, wherein said metallic salt contains a metal selected from the metals of Groups Ia, IIa, IIb of the Mendeleev Periodic Table of Elements.
2. The composition of claim 1 wherein said ethylene polymer is an ethylene copolymer.
3. The composition of claim 2 wherein said ethylene polymer is ethylene-vinyl acetate copolymer.
4. The composition of claim 2 wherein said ethylene polymer is ethylene-alkyl acrylate copolymer.
5. The composition of claim 4 wherein said ethylene-alkyl acrylate copolymer is ethylene-ethyl acrylate copolymer.
6. The composition of claim 1 wherein said talc filler is coated by mixing the talc, metallic salt of fatty acid, and ethylene polymer together in a mixer.
7. The composition of claim 1 wherein the ethylene polymer is curable.
8. A composition useful for coating wires or cables, consisting essentially of:
(a) ethylene polymer, (b) about 2.5 to about 150 parts by weight, per 100 parts by weight of ethylene polymer, of talc filler coated with at least one metallic salt of a fatty acid having 8 to 20 carbon atoms, wherein said metallic salt contains a metal selected from the metals of Groups Ia, IIa, IIb of the Mendeleev Periodic Table of Elements, and (c) conductive carbon black having a high specific surface area.
(a) ethylene polymer, (b) about 2.5 to about 150 parts by weight, per 100 parts by weight of ethylene polymer, of talc filler coated with at least one metallic salt of a fatty acid having 8 to 20 carbon atoms, wherein said metallic salt contains a metal selected from the metals of Groups Ia, IIa, IIb of the Mendeleev Periodic Table of Elements, and (c) conductive carbon black having a high specific surface area.
9. The composition of claim 8 wherein said ethylene polymer is ethylene copolymer.
10. The composition of claim 9 wherein said ethylene polymer is ethylene-vinyl acetate copolymer.
11. The composition of claim 9 wherein said ethylene polymer is ethylene-alkyl acrylate copolymer.
12. The composition of claim 11 wherein said ethylene-alkyl acrylate copolymer is ethylene-ethyl acrylate copolymer.
13. The composition of claim 1 wherein the metallic salt is a stearate.
14. The composition of claim 13 wherein the metallic salt is calcium stearate.
15. The composition of claim 13 wherein the metallic salt is zinc stearate.
16. The composition of claim 1 wherein the metallic salt is present in an amount of from about 0.05 to about 5.0 parts by weight per 100 parts by weight of talc.
17. The composition of claim 1 wherein the metallic salt is present in an amount of from about 0.5 to about 2.0 parts by weight per 100 parts by weight of talc.
18. The composition of claim 1 wherein the talc is present in an amount of from about 10 to about 25 parts by weight per 100 parts by weight of ethylene polymer.
19. The composition of claim 1 wherein the talc is present in an amount of from about 25 to about 45 parts by weight per 100 parts by weight of ethylene polymer.
20. The composition of claim 1 having a flame retardant additive in an amount sufficient to render said composition flame retardant
21. The composition of claim 20 wherein the flame re-tardant additive is present in an amount of about 0.5 to about 100 parts by weight per 100 parts by weight of ethylene polymer.
22. An electric wire or cable insulated with a cured composition consisting essentially of ethylene polymer and at least about 2.5 to about 150 parts by weight, per 100 parts by weight of ethylene polymer, of talc filler coated with at least one metallic salt of a fatty acid having 8 to 20 carbon atoms, wherein said metallic salt contains a metal selected from Groups Ia, IIa, IIb of the Mendeleev Periodic Table of Elements.
23. An electric wire or cable having a conductive shield consisting essentially of ethylene polymer, conductive carbon black having a high surface area and at least about 2.5 to about 150 parts by weight per 100 parts by weight of talc filler coated with at least one metallic salt of a fatty acid having 8 to 20 carbon atoms, wherein said metallic salt contains a metal selected from Groups Ia, IIa, IIb of the Mendeleev Periodic Table of Elements.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80089977A | 1977-05-26 | 1977-05-26 | |
| US800,899 | 1977-05-26 | ||
| US89956378A | 1978-04-27 | 1978-04-27 | |
| US899,563 | 1978-04-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1115044A true CA1115044A (en) | 1981-12-29 |
Family
ID=27122271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA303,203A Expired CA1115044A (en) | 1977-05-26 | 1978-05-12 | Polyethylene composition containing talc filler for electrical applications |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5416553A (en) |
| AU (1) | AU524422B2 (en) |
| CA (1) | CA1115044A (en) |
| DE (1) | DE2822817C3 (en) |
| FR (1) | FR2401192B1 (en) |
| GB (1) | GB1601043A (en) |
| IT (1) | IT1096232B (en) |
| NL (1) | NL184628C (en) |
| NO (1) | NO150377C (en) |
| SE (1) | SE443678B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3210726A1 (en) * | 1982-03-24 | 1983-10-06 | Bayer Ag | CABLE SHEATHING |
| US5335697A (en) * | 1991-10-25 | 1994-08-09 | Carol M. Botsolas | Pipe insulation end cap |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3334063A (en) * | 1965-06-29 | 1967-08-01 | Gen Electric | Insulating material |
| US3617377A (en) * | 1966-06-10 | 1971-11-02 | Fujikura Ltd | Insulation consisting of ethylene-propylene rubber composition for electric wire and cable |
| GB1103099A (en) * | 1966-06-24 | 1968-02-14 | Phelps Dodge Copper Prod | Improvements in or relating to shielded electric cable |
| JPS5428960B1 (en) * | 1968-01-22 | 1979-09-20 | ||
| CA1004386A (en) * | 1971-06-14 | 1977-01-25 | National Distillers And Chemical Corporation | Fire retardant polymeric uni-insulation compositions |
| JPS4892444A (en) * | 1972-03-13 | 1973-11-30 | ||
| US3922442A (en) * | 1972-06-01 | 1975-11-25 | Nat Distillers Chem Corp | Flame retardant compositions |
| US3960739A (en) * | 1973-06-21 | 1976-06-01 | General Electric Company | Method of stabilizing the dielectric strength of polyolefin polymers, and the stabilized compositions and products thereof |
-
1978
- 1978-05-12 CA CA303,203A patent/CA1115044A/en not_active Expired
- 1978-05-24 AU AU36422/78A patent/AU524422B2/en not_active Expired
- 1978-05-24 DE DE2822817A patent/DE2822817C3/en not_active Expired
- 1978-05-25 NO NO781829A patent/NO150377C/en unknown
- 1978-05-25 JP JP6178678A patent/JPS5416553A/en active Granted
- 1978-05-25 NL NLAANVRAGE7805716,A patent/NL184628C/en not_active IP Right Cessation
- 1978-05-25 IT IT23806/78A patent/IT1096232B/en active
- 1978-05-25 GB GB22624/78A patent/GB1601043A/en not_active Expired
- 1978-05-25 SE SE7806039A patent/SE443678B/en not_active IP Right Cessation
- 1978-05-25 FR FR7815535A patent/FR2401192B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT7823806A0 (en) | 1978-05-25 |
| NL7805716A (en) | 1978-11-28 |
| NL184628C (en) | 1989-09-18 |
| IT1096232B (en) | 1985-08-26 |
| NO150377B (en) | 1984-06-25 |
| DE2822817A1 (en) | 1978-11-30 |
| SE7806039L (en) | 1978-11-27 |
| NO781829L (en) | 1978-11-28 |
| GB1601043A (en) | 1981-10-21 |
| NO150377C (en) | 1984-10-03 |
| NL184628B (en) | 1989-04-17 |
| AU524422B2 (en) | 1982-09-16 |
| DE2822817C3 (en) | 1982-04-01 |
| AU3642278A (en) | 1979-11-29 |
| FR2401192B1 (en) | 1985-09-27 |
| JPS5416553A (en) | 1979-02-07 |
| JPS5711570B2 (en) | 1982-03-05 |
| DE2822817B2 (en) | 1981-07-23 |
| FR2401192A1 (en) | 1979-03-23 |
| SE443678B (en) | 1986-03-03 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |