Note: Descriptions are shown in the official language in which they were submitted.
8CX~
~L~5~L~3~ ;
This invention i8 directe~l to an imprsved ~lame
r~tardant polycarhon~ ompo~itioxl of an aromatic c~rbonat~
~ lymer in admixture with an organic alkali m~tal salt or ar~
organic alkalin~ ear~h ~tal ~alt or ~ixtur~s th~r~o~, th~
i~provem0nt whi~h comprise~ havir~q in admixture with th~ poly-
c~rbona~e a ~luorina~ed polyolefin in Bll~f~iÇient ~Iuantity to
r~ndar the polycarb0~ate aompo~itiorl noa~-dripping..
In the art~ th~re ar~ many ~lame retardan~ additiva~
which ~re employed by mixil~g with polycarbo~a~e to re~der ~uch
10 mat~rials ~el~-~x~iaguishing or flame retardant. Suah flam~
r~tardant additiv~s a~e employ0d irl varying an~:>un~ in order to ~ ~ :
b5 e~e~iva in ~x~ingui~hing burni~g o~ tho~0 produc~ which
~ra co~ustiblo.
E~owever, ~ven if th~3 polycarbonate doe~ not burn, in
flamo, it may drip hot particl~ which can iynite material
below it.
It ha~ been ~urpri~ingly discovered tha~ an aromatic
poly~:~rbon~t~ mat~e flame retard~nt by incorporating with ttle
aro~atic polycarbon~ organic ~lkali me~al ~alt~ or organic~
. . .
20 alka in~ e~rth m~tal salt~ or mi~ctvlres ~hsr~oP ca~ ~o rendler~d
non-dripping by ~dmixing the ~lam3 r~t~rdant polycarbonat~
with ~ fluorinat~d polyole~in.
The fluorinat~d polyolo~ins used in this inv~ntion
a~ ~Irip retardia~g ~g9nt8 are ¢ommerc:ially availabl0 or c:an b~
pr~pared by lc~ proco~ , Th~y ar~s whi~o olid~ obt~ine~l by
pDlymeriz2tion of tetrafluoroethyl~neO for exampl~3, ixl aqu~ou~
m~dia with fre~ radical i::atZaly8t;91, 0.g., sodium, potaseium o~
am~llium p~roxydis~alf~a~ at 100 to 1, 000 p~i ~t 0-200~C an~
pref~rably at 20-100 C. See Brubak~r, ~. S . pate~t 2, 393, 967
i~ ued 3uly 23, 1968. Whil~ n~t e~s~tial, i~ i8 pref0;rxed ~o
u~e tho re8i~18 in th~ form o~ relatively larg~ parti~les, e.g~,
of av~rag~ size û~3 to ~ s~ly 0.5 n~,. The~3 axe
~,
,'.
. - . , - ,, , ~ . ~
~ 8CH-1915
~05~L33~ :
better than the usual polytetrafluoroethylene powders which
have pa~ticles o~ from 0.05 to 0.5 millimicrons in diameter.
It is especially preferred to use the relatively large particle
size material because it tends to disperse readily in polymers
and bond them together into fibrous materials. Such preferred
polytetrafluoroethylenes are designated by ~STM as Type 3,
and are available commercially from the E.I. DuPont de Nemour
and Company (TFFLO ~ Type 6).
The amount of the fluorinated polyolefin to be used
can vary widely but usually will be from about 0.01 to about
2.0 weight percent based on total weight of the resin.
The composition of the instant invention may also
include fibrous glass as described in Canadian application of
Charles A. Bialous, John B. Luce and Victor Mark, Serial No.
231,463 filed July 14, 1975 and assigned to the same
assignee as the present invention. Also, the composition of
the instant invention may include the siloxanes described in
U.S. Patent No. 3,971,75~ of Charles A. Bialous, John B. Luce
and Victor Mark, issued July 26, 1976, and assigned
to the same assignee as the present invention. Further, the
instant composition can include both fibrous glass and siloxanes.
The organic alkali metal and alkaline earth metal
salts employed in the compositions disclosed herein are more
fully described and claimed in the following Canadian Patent
applications filed in the name of Victor Mark and titled "A
Flame Retardant Polycarbonate Composition" and each of which is
commonly assigned herewith:
Serial No. 211,443 filed October 15, 1974
~erial No. 211,444 filed October 15, 1974
Serial No. 211,459 filed October 15, 1974
Serial No. 212,991 filed November 5, 1974
-- 2 --
1915
Serial ~lo., ~12t~92 fil~d N~mber 5, 1974
Seri~l ~lo. 212,993 filed ~ov~ r 5, 1974
Sorial ~o. 212,994 file~l ~o~re~er 5, 1974 ;
S~rial lao. 212,995 fil~d ~ovember 50 1974
Serial l~o. 213,014~ ilE3d llov~ r 5, 1974 . -
S~cial ~o. 213,û17 i~ d ~ov~ r 5, 1974 :
Serial ~o. 213,018 ~ 3d l~ov~r~b2r 5, 1974
S~rial ~30. al3, 019 ~ile~ ~7o J~ber 5, 1~74
Sexial ~o. 213,020 ~ d ~aovar~b~r 5, 1974
Serial NoO 216, a83 ~ 3d l~ en~r 16, 1974
Th~ tal ~alt~ of any of ~h~3se applicaltions a~ w011
a~ ~ixtur~ of a~y of the ~n~tal s~lts ~:sf ar~y of th~ appli~:aticsn~
m~y b~ UQ~o Pr~ferr~d Y~1~8 in~lude sodium 2,~ trichloro-
benzenoa~lfo~t~; ~odi~ b~zenesulfQ~at~ odium .
n~phthalen~-2,6-disulfonatet ~Oaiu~ p-io~ob~zene~ul~onate;
~odium 4,4'-dibromobiph~nyl-3-~lfonats; sodium 2,3,4,5,6-
p0~ta~hloro-bet~t~e~e~ulfo~ate; sodi~m 4,4'-diahlorodiph~yl-
~ulfide-3-~ul~on~t~ odium tot~chloro~he~yl~h~r~i~ul- ~ .
onat~5 di~odi~ 494'-dichlor~on~oph2~0~ 3~3'~di~ulfo~ate; ~-~
~o~ium 2,5-diehlorothiophen~-3-sulfonat~s ~dium ~alt of
dipA~nylsul~on~-3-~ulf~nic a~i~; sodiu~ dim~thyl 2,4,6-trichloro
5-sul~isophth~ J pota~iu~ ~alt of the sulfonic acid o~
~ichlorophenyl 2,4,5-trl~hlorob~ ne sulfonate; calcium 8alt
of 2,4,5-tri~hlorobenz~2~ul~ona~ilido-4'-~ulfona~; sodium
~' ~1,4,5,6,7,7 h~xa~hlo~obicyclo~ [2.2.1~ -h~pt-5-~n-s~do-
2~ b~nzeno~ul~onate; di~o~ium h~xa~lu~roglutara~: di~odi~m
. .
~hlor~ilates a~d mixtu~es. Th~e s~lt~ ar0 u~ed 1~ amou~ of -;
fr~ doOl to ab~ut 10 weight p~r~nt b~ed on ths w~ight o~
the aro~atic car~nate ~lym~r ~omp~sition.
Th~ ~ro~ati~ carbona~ polymex~ e~ploy~d i~ th~
practi~ sf thi~ ti~n ~rl3 hoMc~poly~srs ~d COpOlylll~r8 th;~
~re pr~par~d by r~a~ting a dihy~ri~ phenol wi~h a carbo~a~e
- 3
' . '
.
.. . . ... . ~. ,: , , : .,
1915
~OS~38
precu~or" Th~ dihy~xis~ phenol~ that caA b~3 employ~ are
bi3phanol~ such as bi~(4-hydrc~xyph~nyl) m~thane, 2,2-bi~(4-
hydr~xyph~nyl) propane (hereinaf~sr r~erred to a~ bispher~ol-A~,
2, 2-bis ~4-hydroxy-3-m~thylph~slyl) p~opane, 4, 4 bi~ ~4-hydr~Dxy-
pSenyl) h~pta~0, 2-2-bis(4 hy~rcxy-3,5~dic~hloropherlyl) propan~, ;
~, 2-}3is ~4-hydroxy-3, 5-dib~omo~hsr.yl) propan~, ~atc!o ~ dihydri~
phelaol ~ther~ such as bis~4 hyd~oxyph~ylj oth~3r, bis(3,5-
di~ sro-4-hyar6~xyp~enyl) ~ ther, et~.: dihydrc~xydiph~nyl~ ~uch
~ p, p ' -dihy~roxyt~ip!h~nyl" 3, 3 ' -diahloro-4~ 4 ' -dihydroxydiphenyl,
~tc.; dihydroxy~ryl su~ono~ 8us~ EI bi~ ~4~hy~roxyp~enyl~
suli~ono, bi~(3,5-dinaethyl-4-hy~rt~xy~h~nyl) sulfone, ~tc~
dih~roxy ~nzenes, resor~inol, hydroguinon~, balo~ and alkyl~
~ub~titut~d dihydroxy be~zen~s such a~ 1,4-dihydxoxy-2,5-
dichloro~enzene, 1~4-dihydroxy-3~m~thylbenæena, ot~ nd
dihyaxoxy dipheny~ sulfoxid~. ~u~ a~ bis(4-hydroxyphe~yl)
sulfoxiae, bis~3,5-dibromo-4-hydr~xyphenyl) ~lfoxide, et~.
A variety of additio~l dihydric ph~nols aro al~o av~ilable
to pxo~ida carbonate polym~r3 a~d ~r~ disclo$ea in U.S. pa~t~
2,999,835 i~u~d S~pt~ber 12, l9S1~ 3,028,365 issu~d April 3,
1962 ~d 3,1S3,008 is~u~d O¢teb~r 13d ~d64~ Also suitabl3 ~or
p~eparing ~he aromatic ~a~bonat~ polym~rs ax~ cop~ly~er~
pr~par~d fro~ any of the above copolym~riæ~d with h~log~n-
~ontainin~ dihydric phenols ~uch as 2,2-bi~(3,5 dichloro-4~
hydroxyph~yl) prop~na, 2,2-bis(3,5-dibxomo-4-hydr~xyph~nyl)
propan~9 ~c. It is o~ ~o~rs~ pPsaibl~ ~o ~mploy two or ~ore
dif~rent ~ihydric phenols or ~ cop~lym~r ~ a dihydric p~enol
with a glycol or ~ith hydroxy or aaid termi~at0d polyeBter~ or
wi~h a dibasic a~id in th~ eve~ a c~rbonate copolym~r or
interpolymer r~ther th~n a homop~lymer i~ desir~ fo~ use in
th~ preparatiQn of the aromatic carbo~te polymar~ of ~his
i~s~tion. Also employ~d in th~ practice of this in~entio~ ~ay
b~ blends of any of the above ~a~ri~l~ to provide ~he ~roma~ic
- 4 -
. ' ~3C~f-1915
~S~138
carbona~ polym~r~,
~he ca~bonat0 precu~or Alay be ei~hor a carbo~l
h~lide, a carbona~e e~ter or a haloformate. The carbor~yl ~:
h~liaes which can J~e ~mployed h~3r~in are~ carbollyl bxo~i~
carbonyl chloride and mixtur~s ~h~re~ Typic~l o~ tha ~:
aa~bonate~ er3 whi~h ~ay be ~3mploy~d h~rein are diphen~l
~rbonat-3, di- ~haloph~nyl ~ carbGn~tes such a~ di-chloropheny 1 ) :~
carbonats, di- (bromophel~yl) carbon~eO di- (trichlvroph~nyl)
carbon~t~, di~ ribromophe~nyl) carhon~t~, etc., di~ lXylph3~yl)
~:arb~te suc~h as di- (tolyl) car~o~ t~, e~c:., di- (naphthyl)
c~r}:onate, di- (chloron~phthyl) c~rbonate, ph~nyl tolyl carbonate,
chlorophenyl ahloronaph~hyl earb~ s, ~tc., or IRaxture~ . :
theraof~ Th~ haloformal~o~ suitabla ~or u~ herein incluae
bis-halo~or~ dihydric phan~ bi~chloroform~as of
eths~lene glycol, n~opentyl gly~ol, ~lya~hyl~ne glycol, eta.) `~
Whils other c~rbo~ate pr~cur~s3r~ will o~cur ~o thos~D skill~d in
rt, ~:~rboE~yl chloride al~o kllo~n as ph~g~n~ i3 pr~rr~d.
~ inclua~d are th~ ~ly~3rlc IQat;e~ial3 o~ a
dihy~ric phenol, ~ ~licarbo~ic a~ d carboni~: aei~. Th~se
ar~ di~cl~3s0d ~n U.S, patent 3,169,121 i3su~d ~ebr~alry 9, 1965.
The aroma~i~ carbonat~ rs of this irlvent~ on ar-3 -
pr~p~r~d by e~ploying ~ ~ol~cular waight r~gula~o~, an acid
acc~ptor and a cataly~tO The ~le~ular ~eig~t regulats~ which
~y b~ employe~ in ~arrying out th~ prsce~s of thi8 inv~ti~n
i~clud~ ph~ol, cycloh~xa~ol, m~hanol, p~ra-~rtiarybutyl-
phenol, parabromoph~nol, ~tc. Prefe~ably ph~slol :i~ employ4d
a~ 3cular ~0ight regul~tor.
A a3ui~cabl~ aci~ alc¢~ptor may be ei~hsr ~n orga~i~ or
inorgania ~ a~:coptoE. A ~itabl~ oxgallic a<:id a~:ci3p~0r
~ a ~ertiary ami~e and inclu~o~ ~ur:h mat~3ri~l1s a~ pyxidina, ~. .
tri~thylami~a, dimethylanili~a, tributylamine, etc~ 9rh0 :~
inorganic ;acid acceptor ~ay b0 on~ which ~an bo ei~aer a
_ 5_ ;
~C~-lgl5
~S~131~ ~
hydr~xide, a c:arbo~ate, a bicarlDo~ata, or a pho~phat~ or an
~lkali or allcali ~arth matal,
Obvioll~ly oth~r ~ateri~l~ c~ al~o b~ ~mpls~y~3d with
th~s aromatic c~rbo~te polyme~r o~ thi~ invellt ~n and inclu~
~u~ ~at~rial~ a~ a~nti-statia ageIlt~,, pigm6~nts, m~ld relea~e
~g~t~, t~9rmal sg~bilizar~, ultraviolet llght ~talbili~r~,
reinforcing ill~r~ and the lik~.,
The compo~iti~n o~ ventisn i8 pr~par~d by
admixing the arom~ arbonats poly~ex with ~he g~rg~nic alkali
10 ~etal or alkaline ~arth ~at21 salt~ a th~3 fluorinated
p~lyol~fin.
Th~ follcwing ~32arnpl~s are se~ ~orth to illustrat~
more clearly ~h~ principle ana~ prac~ice of thi3 inv~ntion to
th~ killod in ~hs art. U~le~3 ot:herwi~ ci ~ied, whera
par~s or porc~er~t~ ax~ tion~, they a~ part~ o~ per~ent~
by weight.
A pol~¢arbs~nat~ com~ition i8 pr~ rod by esstru~ing
~ homopc lymar o~ 2~ 2~ (4-hy~lroxyph~yl) pr~pane (h~raillaft~s
r~r~d t~ as bi~phe~ol-A) prop~-r~ by roa~ctilsg 0~e~atially
20 oquilGolar a~aoun~ of bi~ nol-~ and phQ~gan~ in ~n organic
medium with triethylami~, sodi~m hydroxide, aAd phe~s~l, ul~der
~ta~lard cc)~di~ion~. Thel xesultislg p~lymer ~ n ~d to an ~:
~xtruder, which ~xtrud~r i~ operat~ld at about 265&, ~lld ~h~
ex~rudat~ i8 co~ut~d into pell2t~
Th~ pell~t~ are th~ll injec~i~sn ~ld~a~l a~ ab~ut 315 C
il~tO ~est bars of about 5 in. by 1/2 in. by about 1/16-1/8 in.
thick. ~rhe t2~t barg (5 for ~e~c:ll a~ditiv~ te~l in th~
Table~) ar~ ~ubj0~:t~d ts~ t6~t proeedure ~3t forth in
Underwrit6~rs ' L~borato~i~3, In~:O Bull~lstar~ 94, su:rni~ag T9~ iEor
39 Cla~iying Materials (h~rei~a~r re~erred to ~ 94~o
In accordanc:e with thi9 t~8~ pro~e~v.reg mat~3rial~ ~ inv~tigated
`':
~-1915 ,~'
~ S~ILgL3
a~ r~ted ~i~her UI.~94 V~0" U~ 94 V I, tJT~-g~ V~ a~ed on ~e
re~ults ~3~ 5 ~psci~0n3. The ~rit3ria ~3r ~ach V ratin~ per -
UL-94 i~ bri~ly ~!18 ~oll Gw8 . .
"~-94 V-ON: -Aver3gs 1ar~ing ~nd/or glowi~g a~ter ; ~ :
ro~o~al o~ th~ ig~ ing ~la~ ~ball
~ot ~xceed 5 ~conds, and n~la o~ tn~
ep0cime~ hall dlrip particle~ whic:h
ignite ~b~orbent cotton.
W~3L-94 V~ P,v~ra~ flamillg ~nd/ox ~l~wing af~r
r~val of the ignitirlg ~l~FAe ahall nc~
exc~0d 25 ~e~o~sS~ a~d one of th~
specimesn~ shall drip partial~3 which
ig~ite absorbe~t ~ to~.
94 V II": Ave~r~ge fla~slg and/or flowil~g a~t~r
r~oval o~ tha ignitia~ fla~o shall not
exceed 25 s~ond~ ;~nd the sp~3dm~n~ drip .
fl~ing pzlrticl~ which ig~it~ ~Ibsorbent . ~
cotton. ; ~ ~.
In ~dditi~n, a t~st bar whic~h l::on~$nua~ ~3 burn for m~re than 25 .
20 ~ ond~ ~te:r remo~l Qf lthe ig~iting ~lamel i~ cla~sifi0d, not
by UL-94, but b~ ~he starld~ds of th~ t inv~ntion, ~ ~ :
3~3 U~ur~ing." Furth~r, UI.-94 r~s~uir~ that all te~t b~r~ .`
r~u~t neod the ~ typ~ rating to achiovs the partacular
rating. Otherwis~ 5 b~r~ rec~iv~ the r~ting o~ th0
~or~t ~i~gl~ kar. For ~x~pl~, if OAe ~bar i~ clas~i~iod :~ .
94 V-i~I an~ esther four (~ r~ cl~3i~ied as
Ul-94 V-9, thell the rating ~Dr ;~11 5 b~ Ul-94 V~
~he r~ult~ ~re 8~ tho !I!abl~3,.
8~ 5
~ ~ ;
~SE
To ~ polyc:arbo~a~e of E:s~mplo I i~ ad~od 0.,5
p~rt~ of ~ 2,~,s-~riahlorcs~ 0~s~ul~Q~at~o l~he
~ix~ur~ i~ ex~ lbd" ~oldod, a~d ~e~t~l in
r as ~ ri~ x~pl~ I .
~ ', :
To th~ polycar~onatQ o~ Exa~pl~ I i~ ~ddod 0.5
p~rts of so~liu~ 2,4JS-trichlorol~n~e~sul~ollat~ ~d 0.05
poly~ tra~ o~hyl3n~a), (~old by ~ t
~o~emo~ d Company Zl8 TEFLO~-6) . 'rh~ ~ix~ure i~ :;
axtrudodl, mold~ a~l tost~d in ~he s;~ae m~anner as
d~cri~d i31 ~x~npl~ ~.
The re~ai~ing COM~ Bre prop~rod by the
~ethod~ o~ Exa~ple~ I to III.
:
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8 CCH-l91
~s~
As can b~ ~een ~rom the ~la~a in ~he Tabl~, wh~n ~he
polycar~onate compo~itions contair~ fluori~ated polyolefin :;~
in addition to the flame retardant additiv~,, the poly-
c:arbs~l-at6~ doe~ not drip an~ r;E~tea ~ither UL-94 V-O,
or Ul.-94 V~
Other flame r~tardan~ addi~iv~ and ~luorir~t0d
pt~lyole~ins c3n be ~Ab~tituted for those o~ ~he T~bla with
3.r r~3~ults.
~t ~ill ~hu~ bo s~30n tha~ the3 objsct~ forth
10 ~bov~ a~ng th08~ ~nade appar~nt ~o~ the p~eoHding
descrîption ar~ ~ficien11 y att3ined and sirlCe~ C0rt in
ahang~s may be Enade in carrying DUt ~he above pro~ and in
~ha co~position 8et forth withou~ depart~ng ~rom the ~ope3 o~
thi8 inve~tion, it i8 int~nd~d ~at all ma~tax~ co~tained in :`~
the abov~ de~Griptiols ~hall be interpr~ted as illu~rativ~
and not irl a limiting ~ens~.
.
; 11 - '
