CA2136720A1 - Short-fiber-reinforced plastic foils - Google Patents
Short-fiber-reinforced plastic foilsInfo
- Publication number
- CA2136720A1 CA2136720A1 CA002136720A CA2136720A CA2136720A1 CA 2136720 A1 CA2136720 A1 CA 2136720A1 CA 002136720 A CA002136720 A CA 002136720A CA 2136720 A CA2136720 A CA 2136720A CA 2136720 A1 CA2136720 A1 CA 2136720A1
- Authority
- CA
- Canada
- Prior art keywords
- short
- fibers
- fiber
- reinforced plastic
- accordance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/06—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of plastics
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Architecture (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Flexible plastic foils reinforced with surface-treated short fibers of approximately 0.3 to 10 mm length, and their use mainly in roof and tunnel construction. Such flexible short-fiber-reinforced plastic foils have very good overall properties, mainly a high resistance to aging, high stress resistance and high mechanical and thermal stability and weather resistance.
Description
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-
~ 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
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 ~ 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, ~-
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 ~ 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, ~-
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 ) 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. . . :
, ::
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
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
- 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 ) 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. . . :
, ::
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
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 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 ) 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.
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.
' ~'; ' '
~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 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 ) 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.
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.
' ~'; ' '
Claims (21)
1. A short-fiber-reinforced plastic foil, characterized in that it is flexible and consists of a plastic matrix containing surface-treated short fibers.
2. A short-fiber-reinforced plastic foil in accordance with claim 1, characterized in that the matrix is a thermoplastic material, an elastomer, a thermoplastic elastomer or a polymer blend.
3. A short-fiber-reinforced plastic foil in accordance with claim 2, characterized in that the matrix is a thermoplastic material.
4. A short-fiber-reinforced plastic foil in accordance with claim 3, characterized in that the matrix is a homopolymer made of polyethylene, polypropylene, polyamide, polyester or polyvinyl chloride, or a copolymer made of styrene/acrylonitrile, styrene/butadiene/acrylonitrile or polyvinyl chloride/ethylvinyl/acetate.
5. A short-fiber-reinforced plastic foil in accordance with claim 4, characterized in that the matrix is a plasticized polyvinyl chloride, ethylene vinyl acetate grafted with polyvinyl chloride or an ultra-low density polyethylene.
6. A short-fiber-reinforced plastic foil in accordance with one of the claims 1 to 5, characterized in that the surface-treated short fibers have a length of 0.3 to 10 mm and a diameter of 5 µm to 1 mm.
7. A short-fiber-reinforced plastic roil in accordance with claim 6, characterized in that the surface-treated short fibers have a length of 1 to 6 mm.
8. A short-fiber-reinforced plastic foil in accordance with one of the claims 1 to 7, characterized in that the foil contains 1 to 40 weight-% of surface-treated short fibers.
9. A short-fiber-reinforced plastic foil in accordance with claim 8, characterized in that the f oil contains 2 to 16 weight-% of surface-treated short fibers.
10. A short-fiber-reinforced plastic foil in accordance with one of the claims 1 to 9, characterized in that the surface-treated fibers are synthetic fibers or textile fibers.
11. A short-fiber-reinforced plastic foil in accordance with claim 10, characterized in that the synthetic fibers are boron fibers, glass-ceramic fibers, glass fibers, carbon fibers, metallic fibers or rock fibers.
12. A short-fiber-reinforced plastic foil in accordance with claim 10, characterized in that textile fibers are aramide fibers, polyvinyl chloride fibers, polypropylene fibers, polyphenylene sulfide fibers, polyetherimide fibers, polyamide fibers, polyimide fibers or polyester fibers.
13. A short-fiber-reinforced plastic foil in accordance with claim 11, characterized in that the short fibers are glass fibers.
14. A short-fiber-reinforced plastic foil in accordance with one of the claims 1 to 13, characterized in that the short fibers are surface-treated with epoxy silane or amino silane.
15. A short-fiber-reinforced plastic foil in accordance with one of the claims 1 to 14, characterized in that the foil additionally contains one or more additives in an amount of 0.1 to 70 weight-%.
16. A short-fiber-reinforced plastic foil in accordance with one of the claims 1 to 15, characterized in that the plastic matrix contains approximately 44 to 55 weight-% of plasticized polyvinyl chloride which contains approximately 2 to 16 weight-% of surface-treated glass fibers of a length of 3 to 6 mm and approximately 35 to 45 weight-% of at least one additive selected from the group consisting of plasticizers, stabilizers, co-stabilizers, lubricants, fungicides, and modifiers.
17. A short-fiber-reinforced plastic foil in accordance with one of the claims 1 to 15, characterized in that the plastic matrix contains approximately 75 to 80 weight-% of ethylene vinyl acetate grafted with polyvinyl chloride, which contains approximately 2 to 10 weight-% of surface-treated glass fibers of a length of 3 to 6 mm and approximately 10 to 20 weight-% of an additive selected from the group consisting of plasticizers, stabilizer, co-stabilizers, lubricants, fungicides, and modifiers.
18. A short-fiber-reinforced plastic foil in accordance with one of the claims 1 to 15, characterized in that the plastic matrix contains approximately 90 95 weight-% of ultra-low density polyethylene, which contains approximately 2 to 5 weight-% of surface-treated glass fibers of a length of 3 to 6 mm and approximately 2 to 5 weight-% of a modifier.
19. A method for producing a short-fiber-reinforced plastic foil in accordance with one of the claims 1 to 18 by means of a calender method.
20. A method of use comprising using the short-fiber-reinforced plastic foil in accordance with one of the claims 1 to 18, for constructing a roof or tunnel.
21. A method of use comprising using the short-fiber-reinforced plastic foil in accordance with one of the claims to 18, as a seal for landfills, water reservoirs, tank linings and water protection.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH01304/93A CH689035A5 (en) | 1993-04-29 | 1993-04-29 | Kurzfaserverstaerkte plastic. |
| CH1304/93-9 | 1993-04-29 | ||
| EP94105752.3 | 1994-04-14 | ||
| EP94105752A EP0622172B1 (en) | 1993-04-29 | 1994-04-14 | Plastic film reinforced with short fibers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2136720A1 true CA2136720A1 (en) | 1994-11-10 |
Family
ID=25687265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002136720A Abandoned CA2136720A1 (en) | 1993-04-29 | 1994-04-28 | Short-fiber-reinforced plastic foils |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH08505182A (en) |
| AU (1) | AU6649894A (en) |
| CA (1) | CA2136720A1 (en) |
| CZ (1) | CZ330794A3 (en) |
| WO (1) | WO1994025253A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005200465A (en) * | 2004-01-13 | 2005-07-28 | Bando Chem Ind Ltd | Polyolefin resin film and its manufacturing method |
| EP2594397A1 (en) * | 2011-11-15 | 2013-05-22 | Sika Technology AG | Membrane with surface structure |
| US10265890B2 (en) * | 2015-04-10 | 2019-04-23 | Channell Commercial Corporation | Method of manufacturing a thermoset polymer utility vault lid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3869306A (en) * | 1964-09-22 | 1975-03-04 | Owens Corning Fiberglass Corp | Glass fiber reinforced elastomers |
| FR2507123A1 (en) * | 1981-06-04 | 1982-12-10 | Arjomari Prioux | Reinforced thermoplastic semi-finished sheet prod. - prepd. from poly-aramid pulp, thermoplastic powder or fibres and opt. binder, for thermo-forming or stamping |
| US4595620A (en) * | 1984-07-23 | 1986-06-17 | The Dow Chemical Company | Dead-folded articles from fiber-reinforced plastics |
| JPS63265609A (en) * | 1987-04-24 | 1988-11-02 | Dainichi Color & Chem Mfg Co Ltd | Reinforcing material and r-rim polyurethane molded item |
-
1994
- 1994-04-28 JP JP6523890A patent/JPH08505182A/en active Pending
- 1994-04-28 CZ CZ943307A patent/CZ330794A3/en unknown
- 1994-04-28 WO PCT/EP1994/001346 patent/WO1994025253A1/en not_active Application Discontinuation
- 1994-04-28 AU AU66498/94A patent/AU6649894A/en not_active Abandoned
- 1994-04-28 CA CA002136720A patent/CA2136720A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CZ330794A3 (en) | 1995-06-14 |
| JPH08505182A (en) | 1996-06-04 |
| WO1994025253A1 (en) | 1994-11-10 |
| AU6649894A (en) | 1994-11-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 20000428 |