Note: Descriptions are shown in the official language in which they were submitted.
94/25253 ~13 6 7 2 0 PCT/EP94/01346
S~ORT--~IBER~ FoR~ED PhAST~C ~OII,S
~ D 0
The pres~nt in~r~tion ~elates to ~ ~lexible plas~
~oil r~inforced ~i~ s~face-trQated ~ho~ rs, a process
for its production ;~nd it~; use.
Non-r~in~orc~d as ~Qll asl reinforc~d pla~;~ic f oils
are u~ied ~Eor t~e mo~ di~Qrse pu~ es ~n tha fie~d of
building ~terial~ ( f os~ exa~ple, ~ee S~A ~ Swis~ E~gine~r~ and
Architec:ts A3gocia'cion~ Standard 280 tl983)).
~ o~e~r~r, ~on-relnforced pla~tic: foil~ hava
disad~antag~ or ex~ple, t~ey c:an ha~e hig~ s~r~r~age
value6, they have a larg~ t~er~al.expan~io~ coeffici~nt, ~o~e
hav~ a lack of ~o~cing prope~tie~ or e~ample in weldir~g),
and may ha-v~ only a mediocre stre~. ~h~ r~ult of thi~
~at the~r u~e, ln particula~ in coN~ection with ~ealing and
in6ulatior~ ~uc~ n roo~ and tunnel construc~ion, i-~ no~
guite ~ati~f acto~y . l~or ~is r~ason i~ h~s ~en attemp~ed to
reduc~ se disad~antages by D~ea~s of ~ rein~orce~n~nt.
Rein~orce~esl~ o~ the pla~tic ~aterials c~ e provided~ for
example, by wea~e~, ~o~ren fabrics, ox ~leeces of ~;ynthetic ana
ir~os~g~nic fi~r~. ~he purp~ o~ e r~ orc:e~ent~ i~; to
i~proYe the propsrt~es o~ th~ plao~c ~te2~ials. For example,
latti4e-rein~orc~ad plasti.c ~oils ar~ u~d ~n th~ d o~
~ulldil~g ~aterials, w~ich con~ Or a wo~ren fa~rtc, wQave or
le~ce b~twe~n the ~o~toD~ and top~layQr ~r ~e ~oil~ Howe~rer,
a :r:e~o~c~e~t o~ t~ls type r~quires an exten~i~ e production
prooe~, po6~ t~e danger of del~nat~on and cause~ proble~s
coverlng t~e knots.
To reduce these disad~an~ag~t~ lt lla~ n ~roposed
to e~ed short ~ibers in the plast~ maeerial~ and to o~it t~e
conventional rabric ~einforcement c:~mpletely.
Plastic materials containing con~rentional short
~i~e~s are described for exampl~ by Th. F. Schuler in
"Kautschuk u~d Gummi- Kurlststof~e" ~caoutc~ouc and Plas~
Rubber~, Vol. 45. No. 7, July 1992, pp. 548 - 54~, in "Xevlar
Short Fiber ~einforcement of Elastomer Matric~s". US Patent
CONFIRMATIONCOPY
W0 94125253 2,~36~1~ PCT/EP94101346 ~
4,595,620 disclo~;es a fclded ar~ic:le made of ~hort-~iber-
reinforc~d plastic foil, and Fre~c~ Patent Plablication ~R-A-
2, 5Q7 ,123 descri~e~ a semi-fini~hed product containlng a
thermo~la8ti:: ~atrix with polyamide pulp embedded 'cherein,
wherein a portion of the pulp can be par~:ially replaced ~y
mineral 2;hort fiber~ ~owever, all th~e reinforcements made
with conventional sho~t Si~ers do not ~ati~fact~rily result in
the desired phy~ical and chemic:al properties, in particular in
connection wit~ flexi~l~ plaE~tlc:foil~3 such a~ are employed in
roof and tunnel construction~ In addit~on, adh~35ion problems
be'cween the sho~t fiber~l and ~:he ~atrix occu~ artlcle
entitled "Renforc~ent du PVC Souple par le~ ~ibr~s Santo~eb
W" ~Reirlf orce~er~t of Flexible PYc by Santclweb W Flbers ~ in
"Colaposites, Pla~st;ique~ Ren~orceés, F~bras de Verre Textil~n
~co~po6ite-, Reinforced ~last ~, Text~le Gla~ ers], Vol.
25, No. ~, ~985, pp. 50 to 55 dP~ribe~ ~ur~ac~-treated
cellulo~e fi~er~ in a ~atrtx o~ pla~ticized polyvinyl
chloride. ~oweve~, thi~ r~reno~ does not pro~ide any
i~or~ation ~eyond ~hi9 regardLng:t~e employmen~ of oth~r
~urface-treated ~ort fibQrs and t~elr surface ~reatment.
Y OF TEE ~ ION
~ t i~ t~ere~ore ~n ob~ect of t~ lnvention to
proYide seals or in~ulations, in particul~r for ~ses in roo~
construction and tunn~l construction, whic~ ~o not h~ve t~e
abo~e-mentioned dis~aa~age~.
Thi~ ob~ect i8 a~tainad in accordance with t~e
invention by mean~ o~ a reinfoEced plastic foil, t~e
rein~rcement o~ ~hich is b~6~d on sur~ace-treated 6hort
fibe~s. It was surprisingly ~ound that ~ plastic foil
rei~orced in thi~ way can not onl~ b~ e~ployed in roo~ and
tunnel constructlon, but ~lso does not ~ve any
disad~antageous properties in comp~rlson ~ith t~e kno~n
pla~ic fo~ls ~entioned above and lnstead i~ ~uperior to ~hem
in 80me o~ it~ properties.
94l25~53 ~ ~ 3 ~ 7 ~ ~ PCT/EP94/01346
~ he!3e, and o~he~ obj ects, will be readily understood
by one ~Xllle~ iD t~ ar~, a~; ref erenc~a iE; ~dP ~o the
following dra~ings and detailecl d~scription.
~ ig. 1 illustrate3 an ~bodi~ent of the di~tri~ution
of the ~hor~: *ibQrs in a f oil ~ top view), and Fig . 2
~ llus~rate~ an ~bodi3~lent of t~e di~tribution of th~ short
ibers in a cro~s s~c~ion o~ a f oil .
~ rhus, the in~ ntion :relates to a f lexible ~lastlc
- ~oil xein~orced wi~ sho~ ~i~ers. di~tinguished in ~iat ~t
cos~ta~n a s~ ace-trea~ed a~bitrary ~hort fiber em~ dded in a
~aLtrix ~a~ of a pl~ tic mat~rial,
The pla~tic ~ater~æl of the ~atrix ~hich enclo~;~s
t~ 6Urf ace--tr~ated ~hort f i~ lik~ an en~Qlop~3 can be an
arbit:rary ho~opolysler or ~opoly~er o~ f~sr exa~pleJ a
th~opl~stic ~ater~al, an ~astom~r, a 1:h8~mopl~a~tic
ela~ato~er or a ~oly~er blen~. All thes~ plastics are ~no~m
and ~er~ore can ~ produced in a known Isan~ler, for exampl~ a
polyrea¢tion lcuch as poly~ddition, polyconderlsation and
p~ ation and a poly~a~r-analogouE~ re~ction~
~ her~oplas~s ax~a under~:ood to ~e pla~;tic ~at~riàls
~it~ a line~ or branc~d ~ true:tUr~ . Cited a~ exa~pl~ arç~
homo-poly~ar 8UC~ as polyel:hylen~ of lo~, ~ediu~ or ~igh
density, and ~3pec:~ally ult~a-low den ity, low density
polyethylene ~ith a linear structu~e, polypropylene, polyamide
such a~ Nylon 11 and Nylon ~, polyester, polyvinyl chloride,
e~pecially pl~st~ci2ed polyvinyl chloride, poly-l-butene~
poly-iso~tylen~, iono~er~, polyYinyl~dene chloride,
polym~thyl ~hacrylate, poly~inyl alco~ol, poly~inyl ac~tate,
a3 ~Qll a~ copolymers o~ styreneJacrylonitrile, 6tyr~ne~
acrylonitrllQ and butadl~ne, polyYinyl c~loride/e~hylsne ~inyl
acetate, ethyl~ne/acryllc acid e~ter, et~ylen~/~inyl a~etate,
propylene copolymeriz~d with ot~er ~-olefins such as ethylene
or butene, ethylene/propylenell-butene, Y~nylidene
- 3 -
WO 94/25253 ~ ~ 3 e 7 2 0 i PCTEPg4/01346
chloride/~rinyl chloride, methyl methac~ylat~et~yl acrylate,
a~ well a~; Nylon 6/Nylon 66.
Ela~;tomer~ are generally understood to be slig~tly
cross~ ced plastics . Cited a~ exa~ple~ are: olef inic
~lasto~ers, such as ethyl~ne/propylene copoly~
et~ylene~propylene dien copoly~er, an ethyltY~nyl acetatG
capolymer and a.n ethyl~ne~et~yl acrylate copolymer,
furthermc~re natural and synthetic caout~ou~, styrene-
butadian~ caoutchouc, butyl cAout~:~ouc, nitr~lQ caoutchouc,
~luoride~elastos~r, polyacrylate, polyu~ethans, 5il~ con
caoutc~ouc, polysulf ide t:aoutchouc, chloroprene caoutchouc,
c211Oro-sulfonated polyethylene and chlorinatsd polyethylene.
~ Th~rmopla6tic elas~omer~ are, ~or Qxample, styrene-
butadiene-styrene elast~er, styrene-e~hylene-buten~-styrene,
th~rmoplastic polyurethane elastomer as we~l a~ t~ermoplastic
polye ter and polyamid~ elas~o~ers and polyolefinic
t~ermoplastic ~la~tomers, wherein thQ elastomer component can
~e prQsen~ in partially linked ~or~.
~ inally, polymer b~ends~can be us~d, w~ich ~re
mixture~ of dt~fer~nt polyme~s. ~ntionQd by way of example
are polyvinyl chloride/ethylene-~inyl ~c~ta~e (mixture ratio
approx~matsly 9:1 to 6:4), ~olyvinyl c~loride/vinyl chloride-
inyl ac~tat~ ~iXtUrQ ratio approx$~at~ly 9:1 to 3:7),
poly~inyl chlorid~et/chlorina~ed polyethylene (~xture ratio
approxImately 9:1 to 4:6) and poly~inyl chloride~polymethyl
- ~ethacrylato (mixture ratio approx; m~tely 9: 1 to 8:2).
A theL~oplastic i~ the pref~rred matrix, in
: : p~rticular poly~nyl chloride tP~C~, an et~ylen2 ~inyl acetate
gr~fted w~th polyvinyl chloride (EVA-gPVC~, and an ultra-lo~
d~tns~ty polyet~ylene (U~D-PE).
~ he surSac~-treated shor~ fi~er~ are, ~or ~xample,
man-mad~ flber~ and textile fibe~s.
M~n-made Siber-~ include, for example, boron fiberqt,
~ glass-ces~mic ~l~ers, glass fibers, rock ~iberQ, ~la~ wool or , t
:: whi~kers.
Textile fi~rs inclutde, ~or examplt~, ~ram~e fiber~,
~ polyvinyl chloride fiberct, po~ypropylene ~iber~, polyphenylene
: - 4 -
2 0 . ;
t~ 94/252s3 PCT/EP94101346
sul~ e f iberE;, poly~eri~aid~ f ib~rs, polya~nid~ f iber~;,
poly~ide flber~, polye6~er fi~ers or co~ton ~ber~;. Th~se
Dlay be, ~u~ ~e~d not be, Dlolecularly or longit~dinally
oriented.
All ~ese short fibers :ha~e ~en ~urface-treated.
Thi~3 currace treatme~t ~on~ a thin ~ on t~e ~ib~r~ ich
i~ retzl~ ned on t~s sho~t ~ibers in th~ atrix and which, ~mong
ot~er t~ing~, is re$ponsible ~or.the go~ocl a~he~ion to t~ae
~atrix, i~ nec~s~sary ~ria a ~odi er. These treat~sn~ can be
per~ormed either chemically in a Xnown m~er, ~or example ~y
i~pregnating ~i~ ~ treat~en~ age:nt, or p~y~ically. I~
required, dry~nq i~ e~ently ~erf orffled ~
- Silarle c:ompounds, ~or ex~ple, ~uch a~ amirlo ~3ilanes
or epox~ 3ila~es, or polyuret:~ane or ~u~a~ compounds t~or
aple dexol) ~r~ cons~ide~ed as c~emic~l 'creat~nent agQn~3
( ~ee, f o~ exa~pl e, in t~e saries o'f docum~nts o~ the f irm
DEGUSS~ the No~ 75 of Oct. 1987, entitled "Pigme~te"
~ig~e~ts3 o~ the brochur~ ~'Tex~:ilglas" tTextile Glass~ of~
~Eq'ROTEX) .
Etc31~g of th~ ~ibers, for Pxa~ple, carl ~e mentioned
as a physical treat~ent ~ch is u~ed with carbon fl~rs~ ar~d
ara~aide f i~8 in particular, or meta~liz ing or roughenlng of
~he f~ers.
Tb,e~;e fibe:e5 W~i~ axe u~;~d a~ 2~hort ~iber~; ~a.re a
len~ o~ approx~ataly 0.3 to lO ~, D~ainly 1 to 6 ~,
particularly 3 to ~ ~, a diaDIeter or approximately S ~ to 1
mm a~d in p~rticular a firleness of a~prox~aately 8 to 14 ~m.
~ e ~oun~ of su~ac~treated 8hort f i~r~ in the
pla~tic foil l~es betwsen 1 to 40 ~eight-%, ~a~nly 2 t~ 20 .
wqi~ht-9~ and particul2u~ly 2 to 16 weight-%~ !
T~l6 a~ount, and t~eref ore t~ ratlo of short f iber~ i
to the mat:rix, ~ ~.rary as a function of th~a use made of the
~hort fib¢r-reinforc~d pla6tic foil. ~or axampl~, to obtal2~ i
ag l~igh a~ pos~ible a ~;trength and a high module, more than
15% of sho~t ~ib~r~ are used. But if only ~mproved
dl~en~ional sta~ility i; required, le~s than 5% of ~;hort
~ibers are u~ed. The~e amounts relate ~o the ~mployme~t of
-- 5 --
~ r~ c~
WO 94/25253 1~ . PCT/EP94/01346 ~ .
gl~s f ibers . If short f l~er~3 ~th a d~f ~erent module or
di~ferent streng~h are used, ~hich in addition have a
~if f erent adhesion to the ~atr~x~ ~he amt~unt~ of short f i~ers
can changa.
The fiurf ace-treated ~hort f ibers are e~sdded ln the
matrix and are statistically dis~ributed on the top, tl~e
bottom and in ~he centar. They can ~ pre~ent by themse~ves
or D~xed ~ith othe~ surfaca-treated ~hort fibers, euch as
textile fiber and m~tal fibers, or textile fibers and gla~ ;
f ib~s . In ~e caa~ o~ ~ixed ~i~er~ i6 a hybrid
r~inf orceDlent.
The ~urf ace-treated ~3hort f ibers em~Qdded in 'che
- ~atrix are ~ ible as such to t~e nz~ksd eye. ~:'rhs ~urf ac~3-treat~d ehort f ibers are preferably
present ~s indiYidual fiber~, particularly in vie~ o~ the
distributlon.
~hQ preferred fi~er ~5 a ~la~8 ~iber.
By combining different ~aterials (pl~tic ~aterial
o ~h~ matrix and surface-trcated short ~iber~), the phy5ical
properti~s of the indi~idual Components axe exce~ded.
~n addit~on, t~e plastic foil~ reinforce~ ~lth
~urf~c~-treated short ~i~ers can adv~ntagaou~ly contaln
additi~s~ o~ an organic andJor inorganic n ture.
~:: Examples of ~Uch ~ddlti~es a~c;
a. Coloriz~ng additi~ n amount~ of approximately
~ 0.1 to l~ weight-~, such a~ pigmentq, ~ f colored ~ort-
: f~b~r-reinforced plas~ic ~oi}s are des~r~d. Cited by way
of 8xample are lnorganic pigm~nts suc~ a~ ~itaniu~ oxid~,
iron oxi~, lead chrom~te, ~hromium oxide, carbon ~lack
and z~nc oxide, as ~ell as or~a~iC pigments SuCh ~8
chro~ium ophtai~, azo pigmen~8, dlpyro~opyrol~, napht~ol-
AS-pigments, phthalo-cyanine~ qu~nacrldone, derl~ates o~
peryl~ne tetra~ar~onic aci~, aminoan~hsaguinone and
~soindoline pigments; q
. Plasticizer~ in a~oun~ o app~oximately 2S to
40 ~ight~ or exampl~ on the basis of pht~alic acid,
suc~ a~ dit2-ethylhexyl)phtbalate, diisooctyl phthalate,
9412s253 ~ 1 3 6 7 2 0 PCT/EW4/01346
di (n-oetyl) p~Lala~e, di-n-aL~yl ph'chalate, 6uch a~;
dl~aethyl ph~ala~, di~thy~ phthala~s r di-propyl . .
phthalate, dibutyl phthalate, diisobutyl pht~alate,
bu~ylbenzyl phthalate, dipentyl phthalats, dih~xyl
p~t~alat~ and d~ isoheptyl phthal~te~ diisono-ayl
phthalate, di(n-nonyl)ph~l~t~, di~sodes:yl phthalate,
di~n~ecyl phthalat~, dii~ot~idecyl ph~ala~,
dicyclohexyl phthalate, diphenyl phthalata,
di~et~oxyglycol pht~ butoxylglycol p~chalate and
di (methylcycloh~ p~thalate; ~ur~er~ore pla~ticizers
o~ ~he ~asis of adipic acid, such as bu~ylbanzyl adipate,
benzyl-2-et~ylhexyl aaipate, trii60tridecyl ~di~pate,
di ( 2-~thyl}~ ipate, dii~ononyl ad~ pate, d.ii~decyl
adipate, di~utyl ~dipate, diisobutyl adipate,
di~u'coxy~t~yl ~dipate, dii~ooctyl adipate and di-n-alkyl
adipat~ f plasti~izer~ on the baEii5 0~ azelaic acid, ~uoh
as ~i-2-~thyl21exyl azelate, dii~ooctyl azelate ~nd di-n-
hexyl azel~e; pla~ticize~s on the ~a8if: of sebacic acid,
~uch as dibutyl sebacate, d octyl sebacate, di~et~yl
se~aca ~ ~nd diisode~yl se~acate; a~ ~e~l as plasticiz~rs
on ~he ~a~i~ of p~o6phonic acid, suc~ as triaL~cyl
phosphate, ~o~ example tri~uty~ phosphate~ (2-
e:t~ylblltyl ) phosphats, tri t 2-ethy~ p~osphate,
~ichloroethyl phosphatE, 2-ethylhexyldiphenyL phosphat~,
cre~yldiphenyl phosphate, tr~aryl p~o6phzl~es ~lch a~
triphenyl phosplaat~a and arylalkyl pho~p~ates, such as
t~ propylphenyl pho~p~at~ and tx~ yl phosp~ate;
c. nm~lcides in aD~ounts of app~roY~mately 0.1 ~o 2
~ight-%, ~uch as lC,lO-oxy-bis-ph~noxyar~ne, N- .
(trihalOgQnomethylthio)-ph~halimide, diphenyl antlmony-2- .
~thyI~exanoate, copper-bi~ hydroxy quinoline) and
tri~utyl oxide and dQr~at~
d. F~ller mat~rial~ in amounts o~ approximately 0.1
to 50 ~eight-%, ~ainly miner~l materials ~uch as
carbonates and silicates, such a~ calc~um, ba~ium
sulfate, calciu~ ~ulfate and aluminum ~ydroxide;
2 ~36720
W094/25253 PCT~W4/013
e. Anti-oxidants of known type~ in amoun~s o~
approx~m~t~ly 0.05 to 3 weight-~, ~ainly o~ the type of
s~erically hLndered phenol~ t ~scondary aro~atic a~ines,
thioether, pho~phite and phosphonite;
f. ~ight-~tabilizers in amount~ o~ approximately
O.1 to 3 weight-~, such a~ o-hydroxyphenyl-ben20- '
triazole~, o-hydroxyphenyl triazine~ an~ o-hydroxybenzo- ;
phenones, a~ well as those of the t~p~ o~ sterically
hindered amines (~ALS);
g. FlaNe-retardants in a~ount~ of ~pproxim~tely 0.1
to 63 weig~t-%, 3uCh 2g a~tY~ony trioxids, alu~num
trihydratc, ~agnesiu~ ~ydroxide an~ magnesiu~ oxid~,
p~osp~oric.acid ester, chloropa~a~in,
d~brom~pentaery~hritol, hexac~lo~ocy6l0pentadien~,
octa~ro~odiphanyl e~her, po~ydibro~ophenylane oxide and
tstra~ro~obi~p~enol-A,
h. Stabilizers ~n amounts of approxi~atsly 1 to ~
wei~ht-~, suc~ as Ba/Zn, BaJ~d, Ca~n ~tabilizer~ in the
rOrm o~ ~al~ o~ organic acids a~d inorg~nic ~cids, ~uch
as Ba/Cd carboxylate and Ca~2n car~oxylate or su~stituted
phenol~; organotin ~tab$1izers, amLnocro~onic acid ester,
2-phenyl$ndole, phenylure~, dlpbRnylthio ~rea, ~b soaps.
met~yltin mercaptide, di-n-oc~ylt~n ~srcaptide an~
a~inocar~vnic acid e~ter;
i. Co-~tab~lizer~ in amounts of ~pproxi~ately 1 to
S ~eiyht-%, 8u~h as organ~c pho~phit~, epoxidizsd fatty
acid e~ter, ~uc~ as ~poxidized ~oyb~n oil, epoxidized
ca~tor oil, ~poxidised lin~eed oil, epoxidiz~d ~unflover
oil, also ~orbin, trismethylol-propane, dipenta2rythritol
an~ penta~rythritol,
k. Mod~f ier6 in amounts o approximate~y ~ to lo
weight-%, such as glycidyl ~etbacrylate (G~A), polymet~yl
~etb,acrylate ~), etbylene vinyl acE~tate (E~JA), ~inyl
chlo~idsJet:~ylene-~inyl ~c~tate co-pol~er, chlorinat~d
polyethylene, acr~lnitryl I butadiene/ ~tyrene graf t
poly~er, vlnyl chloride/ ~cry~e~ter gra~t polymer,
methylmet~acrylate~butadiene/;styrene graft polym~r, ~-
- 8 -
4/2s253 PCT/EP94/01~46
~et:hyl~:tyrene/acrylnitrile ~x-~S/AN3, polyur~thane (PU),
EYA with r~acti~rQ 0~, polyolefins and polyole~in co- and
'cerpoly~er~ chemically modif l~d ~it~ ~aleic acid
an~ydride tM~), and
1. Lubricant~ in a~n4u~ts o~ approxl~ately 0.1 'co 2
veight-~, sllch as calc~um laurate, calciu~ stearate,
calcitam; arachina~ and calciu~-12-oxy~t~reate, a~ ~ell as
the o~e~i;ponding tin, 2inc and magne3iu~ ~alts.
- All ~hRse additîY~6 can ~4 pr~ee~t alon~ or mixed
vi~h aac~ ot~ or exa~ple two or several ~aodi~iers ~hich
ar~ dif ~en~ ~ro~ eaeh other, ln a to~al ~nou~t of O. 1 to
70. O ~eîght~, preferably 2 t~ 45 w~igh~-%, re~Qrring to the
- ~otal amount o~ tbe foil.
Short-fi~er-reinforc~d plaE~tic foil~ of the
in~sntion which are of par~icular in~erest for t~eir tachnical
use include approximately 44 to SS weight-% o~ pl~sticized
polyvinyl chl~ride a6 t~e plas~ic ~natrix, whic~ contai~s
approx~ately Z ~ 16 weigh~-% o~ surfac~ treat~d glass fibe~s
o~ a l~ng~ o~ 3 to 6 ~m, and as an ad~itive approxi~ately 35
to 45 ~reight-~ of ma~nly pla~;'cici2er~, stabiliz~r~, co-
stabilizers~, lubricants, fungicides as~d, if raquir~d,
~odi~ier; also a plastic ~atrix con~aining ~pproxi~ately 75
to 80 ~e~ght-~ o~ ethylene vinyl acsta~e grafted with
poly~inyl chloridOE, approximately S to 10 ~elght-% ~ sur~ace-
treated glas~ ~lbor~ o~ a lengt~ o~ 3 to 6 ~ and
approxL~atel~ 2 to 20 weight-% o~ ~n ad~iti~e, mainly a
6tabilizer, co-~tabilizer, lu~ricant, fungicide and, i~
required, a modi~ier; as ~all a6 ~ plastic ~atrix o~
approxi~at~ly ~0 to 95 ueig~t-S of ultra-l~w d~n3~ty
pol~et~ylen~ conta~ning approximately 2 to 5 weight-% of
surfaae-trcated gla~ fibers of a length o~ 3 to 6 mm and
approximately 2 to 5 weight-S o~ an additive, ~ainly a
mo~ifier.
Th~ short-fib~r-reinfo~ced plastic foil Q~ the
in~ention is primarily a -~oft, ~lexi~le, economically
advantag~ou~ structure having exc~l~ent overall properties, Or
which an excellent dimensional ~tability, ~lg~ aging
_ g _
.~13~720
WO 941252~3 PCT/EP94/01346 ~
resig~arlc~ ~rery good ~eatheri~g., imperm~ ility t~ moisture,
~igh load-carryirlg ab~lity ( important ~ith ground Yater seals,
for exampla), abil~ty to withstand beir~g llralked on, resi~tance
to c~emir:al ~ffect, ~ainly great mechanical stability and
thermal stability, great ten~ile ~trengt~, low ~aodule of
elasticity, permeability to ~ater vapor, low coef~icient of
elongation, littl~ ~hris~lng, very good re~ tance to
microorganis~, a}~ility of the foil to be recycled and good
mechanical attachment and adhesiveness should be mentioned.
Further~ore, t~is structure i~ sta~7la o~rer a lengt~ of time
fxo~ loY temperatures (-30-) to ~igh tempera~ 80-C); ~t
prlmarily ha~3 increa~ed tearing rQsista~cs along Yi~,
- simultaneou~ greater s~re~ching, which result~ ~ n an
i~oprove~ent of the total dynamic charactsristic~ of the ahort-
f iber-re~n~orced plas~ic ~oil structllre o~ the in~rention .
Ma~ufact lre of the shDrt-f iber-rein~orced plast~c
foil caD be per~ormed in aecos~da~cs ~i~h kno~ proc~sses, such
as compres~ing, casting or calendering, e~usion, blowing,
dra~ing or brus~ing proce ~;e~i. After manU~ac:ture~ ~Le short-
rei$l~orced plast~: foil i~ pre ~abricated in the
fac~ory pri~arily into the for~ o~ rolls or ir~to tarpaulins.
T~e prQf erred process i~ t~e calendering ~rocs~s .
Wit~ ~his procesa, for exaD~ple, the ~tr~c components trOr
example, 5-Pt~C po~d~sr), ~e ~urface-treated Q~lO~t; ~iber~ a~d,
i~ reguired, ~e additi~res ara f~rst irlti~ately ~xad in
?ccordance ~it~ ~e dry ~lend met~od in a hot mixir~g d~vice
~hll~ stirring at a temperature of approx~ately 110C to
13 0 C f or approxlmately 8 to 12 ~inu~es and ~e dry ~lend i~
prepared. How~ver, t:he sur~ace-tre~t~d short f i~ers can also
b~ directly placed into the compounder or planetary roller
ex~ruder in w~ieh the dry blend (~or exa~ple S-PVC po~der and -~
the additivel;, if r~q~ired) are already pre~ent. A~ter
cooling t~e mixture to about 65~C to 75C in the cooling
mixer, the mixtur~s is placed into a ~ult~-axial compounder or
a multi-a~eial p3anetary roller extrudar in which
plastif ica~ion of the mixture tak~s place at approximatsly
150C to 180-C. Sllbseguently the pla6tified mixtur~ i
-- 1 o -- .,
~131i720 - ! '
~-94/2s~s3 ~ ~ ~ PCT/EP94/0134~
.. ..
con~eyl3d from ths extruder to ths calender and is pas~ed
bet~en t~e ealende~ roller~ at s~ita~le roller pressur~,
t~mperatur~ ~nd spe~d, l~ the course of vhich it ~s provided
~i~ defined t;h~ clsne~s, den~i.ty, tranelparen~r or defined
surac~ e~f~ct:3, sueh as luster, smoot~neas and designs. ~rhe
fis~ ed foil is~ ubse~uently rolled up~ In t~i~ connec~lon
it i~ essential that all component~ ~re homogeneou~ily and
intiT~ately admlxed be~ore entry ~to the calender. Usa of
t~i3 proces~2 doe6 not result in ~,rer~tretch~ ng probl~3m~; which
can occur par~icular~y wlt~ non-rein~orced fOilS.
S~or~-f ~ ber-relrlf orcsd plastie ~oil~; are e~ployed
for the mo~t differen'~ u6e6, CUch aY ~loor and ~all cov~rlngs,
for pipes, hoses, ri~on~: and profiled ~seet~ on~ and
part:ic~alarly as roils t~emsel~e~s, i . e . as t~ln, f lat, webs
which can be rolled up and have 21 ~icknss o~ approximately
O .1 to 6. o m~, mainly O. 8 to 4 mm, for ~lexible seals and
in~ulations t~eat~ cold, ~ound), for example in roo2
construction, tunnel c:on truction, for pool ~;y~ste~s, for pond
sy~tem~, for land~ y~tems, as linings for chemical vat~
and in water protection, for exa~ple as catch ta~in6, dris~king
uater reser~o~rs and tank l~nings.
The 2IdYantages of t~e ~hort-~bOE-r~in~orced plas'cic
f oil in accordance ~ th the in~r~ntion are ob~ous .
T~le capacity oi~ b~ing welded by ro~ots i8
considera~ly i~pro~r~d o~rer tl~at of non-reinSor~ed foils and
the t~szmal expansion coef~icient ~8 lower~d. The di~ens~onal
stability is al60 increased. Reductions in tensile strengt~
are caused by contractions ~hen welding non-reinforced foil3
and in contras~ thereto t e stabiiity o~ the sea~ retained
~hen using short-fiber-reinforced plastlc foiis.
In co~tra~t to foil~ reinforced by latticQ~, woYen
fa~rics, vsbs, wea~e~ or fleeces, all Xnot cov~ring problems
~rQ removed. The adhesion of the fabric to the foil plays a
d~cisive part Yit~ fa~ric-reinforced foils, becau~e poorly
adhering ~abrics lea~ to delamination. Suc~ delamination
problems are completely secondary with -~hor~-fiber-rein~orcad
WO 94l25253 ~13 67 ~ O PCTEP94/01346 ~
pla~tic ~oil ~ of th8 invention, because t~e short ~l~ers are
arlisotropically distributed in t~e ~atrix~
The handling prope~ti@~ and mainly t~ adhesion of
~he short f ibers are consid~rably. i~proved o~er conve~tional
~hort- f iber-r~inforced plastic material~ in accordance wit~
th8 initially c~tsd prior art~ In cont~as~c to th~ ace-
tr~ated cot~on fi~ser~ pl2sticized P~, the pla~t~ c ~oils of
the invsrltion have uni~er~al applicab~lity for the m~st
diver~e eurface-txeated chort f iber~ .
Ha~ cture o~ the s~or1:-~iber-rsinforced pla~tic
foils i6 considsrably 6i~pler ~i~ the calend~3r procsa~.
Ad~ed 'co thi~ that the ~hort-f i~er-reinf orc:ed plast.ic f oils
ar~ ea6ier to recycl~ than a fa~ri ::-rein~orcsd or flaeca- -
reinforced foil. Finally, ~ort~ er-reinforced pl~stic
foils ha~e a le~ er ~volume than lattice-rein~orced foil~
Th~ following example~ illustrate th~ imr~ntion,
without il:6 being 1~ tRd t~ereby.
.
T~e dry blend ~ prepare~l in a hot mixin~ d~rice
(int~rior te3l~perature 120C) ~n acc:ord~nce wi~ch the dry blena
proces6 ~Xunst:~;tof~ Hand~uch PYC: ~PYC ~la~;tic ~andboo)c], part
2, B~c3cerlBraun, 1986, pu~lished by ~an~er-Ye~lag, pp. 832 to
834~ ~roDI the oo~pone~t~ re~ted ~n Table i in t~e percentage
amount~ qt~ed by stirring the~ in ~pproxima~ly 8 to 12
minute~. ~ext, the ~hort ~ib~r~ Gurface-treated with an amino
silan~ compound or an epo ~ ~ilane c~pound are in~roduced
into the hot ~ix~ng de~ice ~i~h t~e a~ount~/1engt~6 also
recited in Tabl~ I under furthar stirring and mixing for
approxi~ately 2 to 4 minutes at 120C. Following cooling o~
the mixture in a cooling mixer to approxi~ately 70C, the
~ixture ls placed into a Buss kneader, in ~hic~ homogenization
and plasti~ication o~ ~he mixture taXe~ place at approx~mately
160C. subcequently the plastifi~d mixture ic conveyed fro~
the extruder to the calender, in w~ich the ~iber-reinforced
foil is made ~ith a desired thickness of o.8 to 4 m~ and a
- 12 -
) 94l252S3 ~ 1 3 6 7 2 0 PCT/EP94lû134~
~dt~ o~ 1 to 2 meters. Next, i~ ~s cooled ~o 25C by cooling
roll~s and is rolled up. . . :
,
::
-- 13 --
WO g4/252~3 ~13 6 7 2 0 ` PCTIEP94/01346 ~ .
T~l,~ ~,
_ ~ - .............................. , ~
_ _ _ _ _ _ A~p~ ~ ~
Addlti~e~ Short ~ ~`
~;xam~10 Com~non~ ~t~1x/ ~rotal ~F$bers
55 ~
_ _ _ . _
Plal t~ ~izer .-
stat~i~lz~r .
2 Co-Stablllzer 38
Lut1r ica~t
F12~,Lc~d~ ~ , , _ ,, ~. ~ ~ - ~
_. . ~C ~ Glaa~ 3 mm 5135~ _ _ _ _ ~, _7
_ 52_ , ___
_ Pla~ iz-r
Stab~lize~r
3 C~-St~billzer 36-
I,ub~lcant
Fu~icid~ _ _ ._ .-
. EC - 10 Glas~ 3 ~un;5135_~ 53 __ 12
. ~ _ .
Pl~ticizer
StabL112ar
4 C!o-Sta~llzer ~ 37
, ~ubrlc~nt
Funaic ~ qe _ ~ _ ___ _
_ ~:c -_10 ~l4~ 4.5 ~ P336 _ _ _ ~0
S-PYC 5o-- __
plaKlc~r
Stab~1120r
S Co-StD~ z8~ ~5
Lu~ric~t
FuncJ~ clde _ . . _ __
EC -- 10 G1A~ 3 m~.5135 _ 15
F
-- 14 --
94125253 ~ 3 5 7 2 ~ PCIEP941013q6
~ .. ~
. . ~ . , . ~ ---- A~Pr~ Ix~ate~_Amou 1~ ~n 9~
. Addlti~s S~ort -
~_I ~atrlx ~otal) F12~=~
_ _ _ __
s-P~c 49 . .-
. _ - _ . __
Pl~ izor
~t~llizer
6 Co--S~ ~-RS ; o~5
Lubr~e~nt
~lc~de~
2~odifler
Pol~t:h~l~e'chn~ r~l ato ~ _ . _ . . _ . _ .
. -- _ EC - lD Glas~ 3 ~ 51~S~ _ _ ~ - _ ~ 6
s-p--vc - - - ---; 4a
Pl~tic~a~
Sta~llzer
7 Co-Sta~lli20r ~3
lcant
PurLgl.cld~
Modif ~r
Pol~et~lm~ a~ 1at~ ) _ ~
_ _ EC --_10 G~3_4 3_mn- 5135~ _ _ _ _ . 9
5-PYC _~ _ . ~6 _
21a~tlei2~r
S~ 112er
8 Co-S~ill2er 40
~: ~ Lubr~c~t
n~,g~cid~
~l~r
~ol ~ ethYl~ethacrylatr~ _.. .. _ _
_ ~ E~: - 10 e~ 3 ~ 5~,,35~_ ~ ~
~: ~VC , _._ ~8_ . _. __.
tlci~
St~lizer
9 Co-St~lll~or ~3
c~t
Fung~ cl~e
r
~Xee2~yl~ thac~ylatef~utadlenRt
: ~t~lrr~n~raft poly~er ) _ -
_ _ ~C - 10 ala~ 4.5 ~m ~335~ _ _ 9
- 15 -
w~ 9412s2s3 h 1 3 5 7 2 O- ` ~ PC'r/EP94/01346 ~=
. _ ~ mae~l ~oUl t ~n ~
. . . ~d~i ~ti~re~ sbo~t
S _ I~trl~ . _ :
_ ~ _- . _
. P1a8e1C~ 2ar
Stab~ r .
~O Cc~~StaLb~l 1 2er 42
Cant
Fu~gl~:ido .
oY
(~athrl~ac~ylat~/~utadl~/
~}=_._ . _ ...
XC -- 10 G1a~B 4 S mS~ P335~ .. . _ _ 11
_~ _ 46
P~B~CL~:~r
s~lli~e~
11 Co-St~lll~sRr 40
LUb~ tc~
~rlgicido
P~
( ~thyl~haeryl tQ/butadl~ae/
~ _ ~
_ _ EC - 10 Claa~ ,,,4 . 5 m~ P~35~ _ 44 _ . . . . ~14
,,, .. _ ,, . ._ . ... - _ . _ .
Pl astS~eizor
~ 1112e~
12 Ct~-Stabll~2~r 40
icant
Jung~
~od l1cr
-- ~ , ..
_ ,_ ~==~ ~_ __
, 51~ .. .
Pli~tl~ r
~ ~ti~ ~ ~s
.3 Co-Stablllzor 39
Lubr~ t
n~nglcldo '
~4e~i~ior ~ Basi~: G~ _ . . . ,
~tGl~JC~791~3~ lo
- 16 - i
~,
~ 94/25253 ~ ~ 3 ~ 7 2 0 PCT~P94/01346 1 ~
. . ~
ADpr~ lxlsna,t~ Amou ~: ln s~_
. Add~tlv~ Short
Exa~Pl~ eom~onent~ ~atr$x t~otal) Fib~r~
_ s3 . .
_ _ _ . ._ - _ _ _ ___
PlLl~t~eLiz~
St~bil~zer
1~ ~-S~ab~llzer 42
~ub~ica~t
Fung~eld~
~od~fier ~3aff~ ~l~h~iStAN~ . . _
__ e~t Gla~ CS 7915 3 ~ ~ . _ ____~L____
9-PVC _ _ 50 .. . _
Pl~t~ciz~r
St~b~llzar
Co-Stab~ er C0
LubricAnt
runglc~de
dif~r_l aa~- AEVA-5HA~ __ _ -. __._. ~ ___ .
. . Cut Cla~ ~S 79~5 3 mm _ _ lO
~ S-PVC . -~ .51 _
: ~lastlcizer
Stabll~2Qr
16 Co-~tablllz~r ~ 39
Lu~rlca~t
: Funglclde
1~ ~dl~ler lBas~ EU~-O~) _ .
~ ~ _ Cut Ola-c CS 1915 3 m~ . _ . ~ _ 10
-~ -PVC 52_ _ _.
. ~ tile~z~ ~
-: St~b~lz~r
i ~7 ~t~bll~or 43
~ c~ . ~
. 1 Fun~ic~d- :
~odi~Qr ~Ba~R P~ _ . .
I . I c~e Gl~- C5 79~5 = l l I 5
- '
: .
~ 17 _
~13 6 7 2 0 PCT/EP94/013~
WO 94l25253 ~ -
.
_ ~, A~ ~x~na'c~ hnou~ ~ ~n ~_
Atd~ t ~ Short
_ ~ _Il-trlx _~Sot~l ) ~ber~
_ _ _ _ __~
, ?9 _ _
Pl~tlC~2~
~ St~lll~ 12
18 S,u~rlc~nt
Fung~cld~
r IB~sa Pl~
_ _ ~ . ~ _
CUt t~ 915 ~ nYn . 9
_~_ ~ . . _. . . , _ _
EV~-cPV~ ~5
. _ _. _ _ .
Plal~tlclzer
Co~ blllz~r 17
_ 19 Lul~ic~t
Fung~.~id~
~lod~f ler ~BR~e _P~ and PHKA) _ .
_ Cut G1~~ CS ~915 3 m~ _ _ .__, 8
~D-P~: 9~S . 5 ___
Xodlf Ler ~Ba~ P15(ql~ _, _ _ 2 5
:~ _ _ ~1~1~ _ _ . 3
.
* EC - ~ype o~ gla~s (~lgh s~licate proportion)
10 = Dia~et~r (~m~ of the individua~ glas~ fi~ers
3 ~ ~engt~ of the individual gl~ f ibers in mm
5136 or P335 -- Sizing (epoxy silane) ~it~ whlch the
t~e gla~; fiber~; ~ore surfa~::e-treated
7915 ~ Sizing (a~ino 6ilan~3 ~ith vl~ich t~le
the qla~ f i~ers vere gurf ace-treated
S-PY~ = Su8pen~ion~ - Poly~inyl chloride
~h~ properties of thq ~hort-iber-re~n~orced foil ~ obtained in accordance ~ith Examples 1 to 12 can be found in
able I~ belov.
ii
1 8
) 9412~2~3 PCT/EP94/01346
f ~
~ 1 3 ~ 7 2 0
~o~oY~o'~o~o~ o~o~o~o~ '
I ~hog ~
~V~3~ ~ ~ ~, o o o~ ~ ~ o~ ~ o
. ~.. _ _ _ _ . _ _ ___
~ aO ~ 8 8 8 8 8 8 8 o o ~ 8
_ _ _ _ _ _ _ _ _ _ _
~, ¦ G ¦ o l ¦ o l ~ ¦ ~ ¦ 8 1 8
'' ~;~ _ _ _ __ _ _ _ _ . . _ ~
S¦ 81 8 ~¦ h¦ ol l 81 l ¦ ¦ ~
~: _ _ __ . _ _ _ _ _ _ - .~
o
~1-36720
WO 94/25253 . PCTEP94/01346
The propOE~ies o~ the s~o~t-fiber-rei~forc~d foils
o~tain~d in accordance w1th EXa~pl~l8 13 to 20 can l;~e found in
Ta~le I~CI below.
?~
.
~ ~ .~ ... , ~ I
~c~p~,o- So~ anc~Sts~c~lng~r Propag~tlonD~nslorl~l
~ 2 ~ ~~ nc~ St2~illty
DIN16730. ~IN 1~734 ~tJo~o %
I DS21 16~34 ~ hrD. 80-C
_ ___. __ I
13 18.9 10.4 6a.2 -0.3
1~ 19 . 1 193 .8 50 . l -0 . 25
~L9.8 13.6 67.2 0.2
I6 23 27.~ 71.6 -0.4
17 18. 7 30 66.4 -0. 3
18 12 . 2 ~42 37. 8 -0 . ~
_ 15~ 20.a3 30.4 61 .a -o. s
L~ _ ~ -- -o.a I
The t~t ~or ~Di~ensional Stab~lity 1~ d
"D~er~;ional Stab~lity 2" in Ta~le ~I ~ere p~rfor~ed as
f ~ w6:
te~t is pe~o~med following th8 ~3tan~z~rd SL~
280 .
:~: Round test bodies ~re ~ta~p~d out rOr ~s purpose,
eir d~mensior~s ars ~ea6urad an~ they are stored a~ 80C for
24 hour~.
A~ter t~ a~ples ~aYe cooled, t~y are again
~eas~r-d and 'ch~ change in d~ameter ls r~ordea.
pime~slo~l Sta~ilitv 2
~ hi~; tQGt i~; per~or~ed ~ f 0110~5:
Rectangular test bodi~s are heated to 80-C, ~solatQd
~nd ~mmediately ~tretc~ed with a force of 200 N.
-- 20 --
s4nszs3 ~ l 3 6 7 2 0 pcT~ps4l~l346
The! ~t~etched ~ample~ are imm~diat~ly coole~ in ice
water and measured~. Subse~uently t~e 5ampl~S are again 6tored
at 80-C for 24 hours and t~e change in length ~ea~red.
ExamE~le 2 ~
A foil of a thictcne~s of 1. 5 mm and a wl~th of 200
c~, produced in accordance with Exa~pl~ 2 wi'ch the additioni o~
10% of EC gla6s ~ibers o~ 3 D~ in len~ 6 rolled out o~
t:he ther~al in~ulation and i8 ~echanically f astened at t~{~
~orners and t:he edgs arsa in ac~-ordance with the pr~csibed
plac:ement ln~tructions. Th~ ~oil webs are weldec~ toget~er
along t~eir long ~ide~ by mean6 o~ hot air.
A~ong oth~r thing6, the f oil placed in t~i~ ~anner
-~zs the following propertie6: high ~V and weatherLng
resistanc~, good mechanical Yalues ( te~s ~ le ~trength t
resistanc4 to tear propagat~on, etc.), ~ery good re3i6tancs to
en~ronmental a~ct6 ~icroorganisms, ~ater, ~nd, e~c.),
pe~m~ability to watcr vapor, good chemical re ~tanc~, ~ery
good d~en~ional sta~ility, capa~ility for recycling and good
flexi~ility v~en cold.
A foil produced in accordance ~ith Ex~mple 3 wit~ an
addition o~ 5% EC-10 glass 4~5 D, a ~idth o~ 200 cm and a
~hi ~ ess of 2.4 ~ i8 fastensd to the ~all of a tunnel with
: : mechanical fa~tenlng pins. T~e long 6ides of the foil~ are
~elded t~geth~r by ~eane of ~ot air. ~n ~his ~ay th~ tunnsl
lin~ng foil protect~ aga$n.at the int~us~on o~ wat~r~
Th~ foil plaaed In thi~ ~anner ~as the ~ollowing
properties, a~ong ~ther~: good mec~anical strength, good
di~ens~lonal stability, good resi6ta~ce to th~ intrusion o~
wat~r, it i8 flame-retardant and capable Or belng recycled.
'
~'; ' '
- 21 -
