CA2383030A1 - Copolymers of aminopropyl vinyl ether - Google Patents
Copolymers of aminopropyl vinyl ether Download PDFInfo
- Publication number
- CA2383030A1 CA2383030A1 CA002383030A CA2383030A CA2383030A1 CA 2383030 A1 CA2383030 A1 CA 2383030A1 CA 002383030 A CA002383030 A CA 002383030A CA 2383030 A CA2383030 A CA 2383030A CA 2383030 A1 CA2383030 A1 CA 2383030A1
- Authority
- CA
- Canada
- Prior art keywords
- antimicrobial
- substrate
- carbon atoms
- vinyl ether
- hydrocarbon radical
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1458—Monomers containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
- C08F291/18—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to irradiated or oxidised macromolecules
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Graft Or Block Polymers (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to antimicrobial polymers which can be obtained by copolymerizing vinyl ethers of general formula (I), especially 3-aminopropyl vinyl ethers, with additional aliphatically unsaturated monomers, and to a method for the production thereof. The polymers can also be produced by graft copolymerizing a substrate, whereby a covalently bound coating is obtained on the surface of the substrate. The antimicrobial polymers can be used as a microbicide coating, among other things, on hygiene articles or in the field of medicine, as well as in paints or protective paint coatings.
Description
FR 08' 28 FAY EGUSSA MARL, IPM , ~~~ CA FETBERSTON ~ I~
CA 02383030 2002-02-21 ' ' >.
C~.Y._, 5a is-WO 1 ._ "
' . .:.
' , '' LODolYm~ra~ of amiaopropyl yinyl ethwrJ: . ~
. , :r.
. '1'hP r r,vRntion ralatco to antiu~i~~ULIdl ~polymeLS : ;..
obtainac~ Ly eopolymerizing aminnfunctionalia~d vinyl . v Pthers with other monomers . The r clvention ; furthErr relates to a process for prepari ng ~thPSa antireicrobis.l , .
' pOlymp.r;l, anrl, to thair uso.
...
' ' .
7.'he inWsntinn further r~lates to antimicrobial polymers ;'.
;
obtainec:. by a. qralL Copolymerizat:icin of . '' ':.
au~inntm;nti on.alized vinyl ethers with other monQmera on a aubstx~atr, and also to a process >for the preparai:i r7n of th~a draft copolymers, and to thoir use.
is It is highly undesirable for bacteria tobecome ~~
establie:hed o.c' 1.o spread on the surfaces of pi~elinas, c:nnf.a r nF rS or, rackaging. Frequently,' slimo layGro .' form ~
and per~:~it slxal.Y rises in microbial populatidns, and ."
.
'Chase can .1 e.~c~ to rersiStent impairm~nL of the ; quality .
l l.u ap~lldc~e of the of water, drinks o1: foods, ally even pr~cimi- and harm to the health of consumers . ' ..
Harr.ari a must ba kept away from all areas of :life in ..
~,rhich h~~giene is iluYu.c~aut,. TliJ.S af'r~~LS Lexllses fo::
direct t.~ody ~nntart, espQCially in ; the geni.tai arAa, and fox the care of thd elcleil~ ~mc.i s.l.c:k. Bdc:l.e.cld utus'L ;, al.SO be kept away from s~~rfac.-PS ' n.f furniture and . ;~i~
' instrumonto in wards, especiaJ.ly in areas for iritenaive Care and neonatal ra rP, r n hnspi tai 1 s, asperi ~ 1 ~l.y ill .
areas fo.r medical ~.nterventivns, and ' ~,n isolatiqn ward's ~
' _ for Cxiz:LCal cases oI mtPrti.on, ~nci ~ I ~~ r n 1-ni ~ ' r.
Pts ' ' ' ~ . v A eutr~ll _ method of treating equipment, or the ~urtar.P<s ..:
' t ~ r:
of furniture or textiles, to resisir bacteria, either: '. '?
3~ wlleu l.lll.~ becomes necessary or else :as a p.rec:ai-i nnary :
:
measure,, is to uac chemicals or solutions or n~ixtuLe:~
. of tlie~a wlllc:h as disinfectants have fairly hri~a~1 anr~
, c~anaral antimicrobial action.
Chemical agents. pf this ' .
~
type act nvns~rec:l.Clcally and are frequently thek~nselve~;
. .
. ; ;;:
.
. ..
.1,r : . A ii f . ii 48!02 42 FR 48' 28 FA7C EGUSSA MARL. IPM ~~~ GA FETHERSTON td 445 ~ . :,:
CA 02383030 2002-02-21 ~ . . , . ,:.
. _ 2 - . . , .,:
.. . , ; ;
~~
toxic r,r i rritant, or form degradatium Y.c~oduclts which are hazardous tu health. In addition, pPn~,le f~equex~tly~
exhibit infi~leranca to thcae materfals once Lyey have " ~' become :yensitize~:l.
' ' ..
. lln.other method t,u counteract surtacR ~preacl of ibacteri.a~ y ' is to i nrnr~orate substancoe with a~ntimicrob~.a~. ac;LZVIi- '4 into a ntatL ix . ~ ' ' ~i a,:
..:.
tort-8ul.ylsminoethyl .lueLtiaerylate is a n~mmarn, a ~.lyi availab_e mnnnmQr in methacrylai:e chomintry aradi is used, ' in paxticulsr as a l~yciLUprillic constituent in ' .~
copOlyme:rizati~ns. For ~xample; EP-E 0; 290 676 ~ .y ..
.dcccribea the uses uL , vdLlous ;polyacryla~es and poZymett~acrylata;s as a matrix for immo~ilixi.ng ~
bactericidal qudl,et~nary ammonium compounds. v ;~.
5:
, : i:
In Fwrothex technical ~ec:lv~c US-A 4 532 269 diSGlOSOS
3 .
,.
tPrpolyrn~r of butyl mcthacrylate, tributyltin ~ :7 ;;
. 20 methacrylate and tent-LuLyldltL,LIlUE3lhyl mel:hac~rylate., ' ~ : :' 'this pa Lymar i ~ used as an ant~.microbial pa,'int fo;r ., :'..
;~hip~ : the hydrophilic test-LuLyld.m~mt.~ell~y.L ;
...
: .
methaCrylate promotPS grariaI Prn~inn of the polymerr v thug liberating the highly toxic tiil~u'tyll.im ~
' Z5 methacrylate as anti mi r.robi a 1 atlent . ~~ , , . ' j n ~ I.
' iu In these applications f.ha rnp~l ymar pr~parr~~l usi.n~~ ~ '';
..:
aminometizacrylatc~ its merely a motri:c ox. carrier ' ~;
substanc~a for added mi c~rc~t~i r.i,t~i~1 ~tc~anl-~ whi~rh. '."
can ';
.
30 dirFuss or migrate out of the carrier aubatance.Sooner ''.
oz ldl.t;r. polymers Of this fiypP 1 C~.~~R ~ fhPi T' i' ~
~tfecti,v;aness onto the "mir~imal in~ibitoxy .' ~~~.
. ;:
CpnC~tiZtisxtiumn (MIC) ' is no longer: achieved on the . , , stlrfacQ _ ' . .' i ; ,, ;.
3 J . ..H
, .;
F,nrnpR~n Patent Applications 0 862 '858 and 0 ;862 85;~ . ':;
have di,~~cluat~c3 Lhat homo- and copolymers oil tert- :.
butyl ami rtnethyl methacrylate, a metk~.acrylatc having . a~ ;
a i . i ~~
' secor~dar';~ arnin.o fi.mc;LlULI, have' inherent micro~biaiclal ' ' . i';
,:
:.
. . . ~r 08/02 02 08 v 2Q FA7C EGUSSA MARL, IPM , ~~~ ~'A FET13ERSTON ItIJ
FR , 00B
' i;.
CA 02383030 2002-02-21 . , ' 'r ~ s ;:
, ' 3 -pzopert iPg _ To avoid undesirable resi,a l.aiic:e phenomena in the microbes, particularly bP~rin~ in rind the '' :
.. .
' development o.f resistance by brx,eLeria k~acm~rn from .
' antibioi:ics research, bystems developer! in thQ ' futura .
will also hive to b~' based on novel compvsi.tiuu~ with 'a;
improvc!1 effectiveim55. ' ' ! .
., A n UE 2 ge~a GJ$ disc;luses antimicrobial pn.i ymar~ :based on ' vinyl E~ther~ grad having a tertiary amino function .
i.
Thoac ~:olymers may Le c~uaLernized before ni- attQr . 'v ..
' polymers. zati ~n . ~ ' !v . . ~ , y ti The Obj~3ct n.f 'the present invention is thorafoxc to . i .
: , dovalop novel pvlymei5 11dV1111J aii'l.lmlcrobial; action .
~ "' ...
which prevent LhP R~tahlishment and~spread of bacteria ' r , on Surfaces. , , a . . a .':
.:
.
Surprisingly, it has now Lkl~dil tuujrd .LlidL c:opolyiteriziny ;, . ami nntnnnt-i n>.zali2ed vinyl ethers with aliph~tically , unsaturated monomeis aud, f espec',.Lively, a~ qraf'C ~t Copolym~:ri ~ati nn r,f these components on a sixbEtrai;c ~;
i gives F ~olymera with a~ 5uZ face .whic:li is durably . .' miCrobiCidal, resists ~~ivPnt~ anr3'phy~iral stresses and doers not exhibit ~ttigrut_:ivii. This means that tllc~Lw~iv ': >:
' 25 is no need for other biocides to be ll,.~',PC1.
,;
, .
3--Aminopropyl W inyl eCher is a c:omniPrrially ava 1 I ah1 .
~ ;:
. product whose preparation, can be found, for. exazqple, in ~~
the European >Jatent Applj ~:ai-.i ~n t) !i1 ~4 7~ (7. TI:
ids usedr tt 1 i~
intwr a~.ia., as an additive for photoreaist systems, . '",;;
daac;ziLea, for example, in (J5 5648 I !~4, nr' ~~ ~n a I
Pment . .a .:
''' ' in the structu.ro of odheaion promoters in specific. ~ i:
. .
., urethane-sildues, described. for examplg, in ;' x i'TS ~.BN~I 3~~2. The use of compounds ' of thit3 'Uype ire antimicr::~bial pulyaet'S 15 not known. ~ I ' d~
.3 1:
' ..
The.. present inv~srWiuci Cherefore provides antimicrobial i ,.
CopolymPis whi eh are obtain~d by copolymcrizir~g a vinyl. ' ~~u !.
ether of the general Lumuuha ' . . " '.
. t.
s ';R
i :
i i .
. . ' ' . i ~i ' . i ' i .
. ;
n, 48/02 l~2 48: 2!d FAX EGUSSA MARL, IPM a~a C.A FETSERSTON I~IQQ'1 FR . '.
., .. , . , ~ 4 - . i . .
::
. . . . . , ..,.
., ;:
I.:
' '. , ;
IH ; . , x ~ ' R . , :., i.
;:
:
O R~~~ . , . .
i . : i:
. R' : i, .
, where Rl is a branc:hPd ~r ~.~nbranchQd hyd~oaarbon ':
~
h radical having from 1 to J G$11J1J1'1 dLUlll3,l .;.
R' is H, and ~ ~ v R3 is H or 3 br~xmched or unbranched hydiuc:a~k~uu iaaic;al having from 1 to h c:arhnn ~tnms,.
a . I . . ii with at leas 1. une al~,phatically unsa~Curated ;
mnnaimar _ ~, i The proFo~:tiom v.C vinyl ethers in the rpac-.ti ;, on ~ m1 xrure .
should t:e from 5 to 98 rnol~s, preferably from '?~
3~0 to 9~7 ~
mold, paztic;ularly preferably from 5~7 to 98 mold, basecY
, on the total of the monomero, in order toy obtai~z i . ;:
suffi~:ie~~~ anLimiCrobial action from the polymer. ,':
, , ;, The aliF~ha~tioally uu5a.~urated monomexs used maY be any monomers whi c~h ar,ter into copolyme~rizati.on th the ~ ~'~' wi ' ;;:
' vinyl ethers of ' tile ~eiacta.l LVrtimlct. Ex.am~les of .
.;.
. suitable monom~.rs are acrylates or rnethacrylatejs, such as acrylic acid, teri=-b~.tyl metha~Ly~.a,te v1: ~t i utdthy=
methacry.late, ~I-yrene, vinyl chloxf.de, vinyl .~thers, ' ' acrylamic~es, ;'' acxylonitriles, ulrrLis (e~Hylraue, ~.
prnpyl Pn~a, htyJ.enQ or isobutylene? ,allyl coajpounds, ' . , ,.
vinyl lseatono9, vinyl a4e'L:ic: acid, ~ vinyl ';.
dL~~.ate or ~
vinyl esters, in pari-.i ~u 1 err, for, examrle, ''' ~ rnothy7. a .
methacry__atc, ethyl methacrylate, butyl methauiyldl.c, lerL-vu~wl methacrylate. methyl . ~r.rylatP, ; ' ethyl .
3O a~ry:~at~, butyl acrylatc, tort-butyl. acrylate;, tent-~ v butylauiiixruetxiyl esters, l-diethylamimnai-hy7.
; !:
mathac,ryl.ata, 2-diethylaminaothy~., vinyl ether, ' .
N 3 ~dietlaylcmimu~L~,pylmethaCrylamide, : 3-mPthac~,'ry~.oyl-i . is n . y ;;
i 1 ~ . ~ 1.
' . ii ' i i . ..
08/02 G~ U8: 2a FA% EGUSSA MARL, IPM ~-- CA FETHERSTON , t~
CA 02383030 2002-02-21 , ..
.. . : i - 5 _ '.
.;
v aminopr~~py1 trimethylammonium chloride, , 2-iacth8cryloy:l-v oxycthyltrimetl~yl~rrtnonium chloride , ~r 2-moth~cryloyl-, , oxyethy.ltr~mPthylammonium mcthoaulf~t'Le.
. ' ~ :
:
. 3 i .
Tt~c: alj phatir.~n i.y ur~saturatod monomers are pz~eLe.cwbly '. acrylic acid compounds ut~ taethaCrylic acid cc~mprnmd~i, dtiti Lhr: vinyl ethers of the general fortn3ula are - preferably 3-aminopropyl vytiyl ether. ~ ;t~
.
The nov~al antimicrobial copolyuel~ mdy be obt3lned . by ;
CopolymE~rizirig vi nyl ethers of the general fordnula, in i ,.
particul ar 3-amznoprvpyl vinyl c~l.rier.s ~ with one ! or mote aliphatical7 y nsaturated 'monomers . ' The polymc~ization ~;
io uocfully a free-r~t~lic;al ~~lytuerization using; a free- .
1.5 radical iniLiat~r or. inducod by radiation. ;Typical it . >:
.
.
procedures are deacriLed lrr Llte examples_ ~ "-.
' , .
The novE~l antimicrobial copolyxttera my~ ~tl3u ".
Lrr ~.bl.dlLleSi ';
by copolymerizing vi ny1 ethers of the gQneral :;'.
,formula, ' ;.
in particular 3-umir~,vpropyl vinyl ether witri t lCd~L
aj one alil'~hatiCal.l y on~aturated monomer on a substrate. .;
''"
Thus giwcc a physisorbad casting ofv thd aritlmlcwuk~idl '1~
' ' copolymer on the substrate.
f
CA 02383030 2002-02-21 ' ' >.
C~.Y._, 5a is-WO 1 ._ "
' . .:.
' , '' LODolYm~ra~ of amiaopropyl yinyl ethwrJ: . ~
. , :r.
. '1'hP r r,vRntion ralatco to antiu~i~~ULIdl ~polymeLS : ;..
obtainac~ Ly eopolymerizing aminnfunctionalia~d vinyl . v Pthers with other monomers . The r clvention ; furthErr relates to a process for prepari ng ~thPSa antireicrobis.l , .
' pOlymp.r;l, anrl, to thair uso.
...
' ' .
7.'he inWsntinn further r~lates to antimicrobial polymers ;'.
;
obtainec:. by a. qralL Copolymerizat:icin of . '' ':.
au~inntm;nti on.alized vinyl ethers with other monQmera on a aubstx~atr, and also to a process >for the preparai:i r7n of th~a draft copolymers, and to thoir use.
is It is highly undesirable for bacteria tobecome ~~
establie:hed o.c' 1.o spread on the surfaces of pi~elinas, c:nnf.a r nF rS or, rackaging. Frequently,' slimo layGro .' form ~
and per~:~it slxal.Y rises in microbial populatidns, and ."
.
'Chase can .1 e.~c~ to rersiStent impairm~nL of the ; quality .
l l.u ap~lldc~e of the of water, drinks o1: foods, ally even pr~cimi- and harm to the health of consumers . ' ..
Harr.ari a must ba kept away from all areas of :life in ..
~,rhich h~~giene is iluYu.c~aut,. TliJ.S af'r~~LS Lexllses fo::
direct t.~ody ~nntart, espQCially in ; the geni.tai arAa, and fox the care of thd elcleil~ ~mc.i s.l.c:k. Bdc:l.e.cld utus'L ;, al.SO be kept away from s~~rfac.-PS ' n.f furniture and . ;~i~
' instrumonto in wards, especiaJ.ly in areas for iritenaive Care and neonatal ra rP, r n hnspi tai 1 s, asperi ~ 1 ~l.y ill .
areas fo.r medical ~.nterventivns, and ' ~,n isolatiqn ward's ~
' _ for Cxiz:LCal cases oI mtPrti.on, ~nci ~ I ~~ r n 1-ni ~ ' r.
Pts ' ' ' ~ . v A eutr~ll _ method of treating equipment, or the ~urtar.P<s ..:
' t ~ r:
of furniture or textiles, to resisir bacteria, either: '. '?
3~ wlleu l.lll.~ becomes necessary or else :as a p.rec:ai-i nnary :
:
measure,, is to uac chemicals or solutions or n~ixtuLe:~
. of tlie~a wlllc:h as disinfectants have fairly hri~a~1 anr~
, c~anaral antimicrobial action.
Chemical agents. pf this ' .
~
type act nvns~rec:l.Clcally and are frequently thek~nselve~;
. .
. ; ;;:
.
. ..
.1,r : . A ii f . ii 48!02 42 FR 48' 28 FA7C EGUSSA MARL. IPM ~~~ GA FETHERSTON td 445 ~ . :,:
CA 02383030 2002-02-21 ~ . . , . ,:.
. _ 2 - . . , .,:
.. . , ; ;
~~
toxic r,r i rritant, or form degradatium Y.c~oduclts which are hazardous tu health. In addition, pPn~,le f~equex~tly~
exhibit infi~leranca to thcae materfals once Lyey have " ~' become :yensitize~:l.
' ' ..
. lln.other method t,u counteract surtacR ~preacl of ibacteri.a~ y ' is to i nrnr~orate substancoe with a~ntimicrob~.a~. ac;LZVIi- '4 into a ntatL ix . ~ ' ' ~i a,:
..:.
tort-8ul.ylsminoethyl .lueLtiaerylate is a n~mmarn, a ~.lyi availab_e mnnnmQr in methacrylai:e chomintry aradi is used, ' in paxticulsr as a l~yciLUprillic constituent in ' .~
copOlyme:rizati~ns. For ~xample; EP-E 0; 290 676 ~ .y ..
.dcccribea the uses uL , vdLlous ;polyacryla~es and poZymett~acrylata;s as a matrix for immo~ilixi.ng ~
bactericidal qudl,et~nary ammonium compounds. v ;~.
5:
, : i:
In Fwrothex technical ~ec:lv~c US-A 4 532 269 diSGlOSOS
3 .
,.
tPrpolyrn~r of butyl mcthacrylate, tributyltin ~ :7 ;;
. 20 methacrylate and tent-LuLyldltL,LIlUE3lhyl mel:hac~rylate., ' ~ : :' 'this pa Lymar i ~ used as an ant~.microbial pa,'int fo;r ., :'..
;~hip~ : the hydrophilic test-LuLyld.m~mt.~ell~y.L ;
...
: .
methaCrylate promotPS grariaI Prn~inn of the polymerr v thug liberating the highly toxic tiil~u'tyll.im ~
' Z5 methacrylate as anti mi r.robi a 1 atlent . ~~ , , . ' j n ~ I.
' iu In these applications f.ha rnp~l ymar pr~parr~~l usi.n~~ ~ '';
..:
aminometizacrylatc~ its merely a motri:c ox. carrier ' ~;
substanc~a for added mi c~rc~t~i r.i,t~i~1 ~tc~anl-~ whi~rh. '."
can ';
.
30 dirFuss or migrate out of the carrier aubatance.Sooner ''.
oz ldl.t;r. polymers Of this fiypP 1 C~.~~R ~ fhPi T' i' ~
~tfecti,v;aness onto the "mir~imal in~ibitoxy .' ~~~.
. ;:
CpnC~tiZtisxtiumn (MIC) ' is no longer: achieved on the . , , stlrfacQ _ ' . .' i ; ,, ;.
3 J . ..H
, .;
F,nrnpR~n Patent Applications 0 862 '858 and 0 ;862 85;~ . ':;
have di,~~cluat~c3 Lhat homo- and copolymers oil tert- :.
butyl ami rtnethyl methacrylate, a metk~.acrylatc having . a~ ;
a i . i ~~
' secor~dar';~ arnin.o fi.mc;LlULI, have' inherent micro~biaiclal ' ' . i';
,:
:.
. . . ~r 08/02 02 08 v 2Q FA7C EGUSSA MARL, IPM , ~~~ ~'A FET13ERSTON ItIJ
FR , 00B
' i;.
CA 02383030 2002-02-21 . , ' 'r ~ s ;:
, ' 3 -pzopert iPg _ To avoid undesirable resi,a l.aiic:e phenomena in the microbes, particularly bP~rin~ in rind the '' :
.. .
' development o.f resistance by brx,eLeria k~acm~rn from .
' antibioi:ics research, bystems developer! in thQ ' futura .
will also hive to b~' based on novel compvsi.tiuu~ with 'a;
improvc!1 effectiveim55. ' ' ! .
., A n UE 2 ge~a GJ$ disc;luses antimicrobial pn.i ymar~ :based on ' vinyl E~ther~ grad having a tertiary amino function .
i.
Thoac ~:olymers may Le c~uaLernized before ni- attQr . 'v ..
' polymers. zati ~n . ~ ' !v . . ~ , y ti The Obj~3ct n.f 'the present invention is thorafoxc to . i .
: , dovalop novel pvlymei5 11dV1111J aii'l.lmlcrobial; action .
~ "' ...
which prevent LhP R~tahlishment and~spread of bacteria ' r , on Surfaces. , , a . . a .':
.:
.
Surprisingly, it has now Lkl~dil tuujrd .LlidL c:opolyiteriziny ;, . ami nntnnnt-i n>.zali2ed vinyl ethers with aliph~tically , unsaturated monomeis aud, f espec',.Lively, a~ qraf'C ~t Copolym~:ri ~ati nn r,f these components on a sixbEtrai;c ~;
i gives F ~olymera with a~ 5uZ face .whic:li is durably . .' miCrobiCidal, resists ~~ivPnt~ anr3'phy~iral stresses and doers not exhibit ~ttigrut_:ivii. This means that tllc~Lw~iv ': >:
' 25 is no need for other biocides to be ll,.~',PC1.
,;
, .
3--Aminopropyl W inyl eCher is a c:omniPrrially ava 1 I ah1 .
~ ;:
. product whose preparation, can be found, for. exazqple, in ~~
the European >Jatent Applj ~:ai-.i ~n t) !i1 ~4 7~ (7. TI:
ids usedr tt 1 i~
intwr a~.ia., as an additive for photoreaist systems, . '",;;
daac;ziLea, for example, in (J5 5648 I !~4, nr' ~~ ~n a I
Pment . .a .:
''' ' in the structu.ro of odheaion promoters in specific. ~ i:
. .
., urethane-sildues, described. for examplg, in ;' x i'TS ~.BN~I 3~~2. The use of compounds ' of thit3 'Uype ire antimicr::~bial pulyaet'S 15 not known. ~ I ' d~
.3 1:
' ..
The.. present inv~srWiuci Cherefore provides antimicrobial i ,.
CopolymPis whi eh are obtain~d by copolymcrizir~g a vinyl. ' ~~u !.
ether of the general Lumuuha ' . . " '.
. t.
s ';R
i :
i i .
. . ' ' . i ~i ' . i ' i .
. ;
n, 48/02 l~2 48: 2!d FAX EGUSSA MARL, IPM a~a C.A FETSERSTON I~IQQ'1 FR . '.
., .. , . , ~ 4 - . i . .
::
. . . . . , ..,.
., ;:
I.:
' '. , ;
IH ; . , x ~ ' R . , :., i.
;:
:
O R~~~ . , . .
i . : i:
. R' : i, .
, where Rl is a branc:hPd ~r ~.~nbranchQd hyd~oaarbon ':
~
h radical having from 1 to J G$11J1J1'1 dLUlll3,l .;.
R' is H, and ~ ~ v R3 is H or 3 br~xmched or unbranched hydiuc:a~k~uu iaaic;al having from 1 to h c:arhnn ~tnms,.
a . I . . ii with at leas 1. une al~,phatically unsa~Curated ;
mnnaimar _ ~, i The proFo~:tiom v.C vinyl ethers in the rpac-.ti ;, on ~ m1 xrure .
should t:e from 5 to 98 rnol~s, preferably from '?~
3~0 to 9~7 ~
mold, paztic;ularly preferably from 5~7 to 98 mold, basecY
, on the total of the monomero, in order toy obtai~z i . ;:
suffi~:ie~~~ anLimiCrobial action from the polymer. ,':
, , ;, The aliF~ha~tioally uu5a.~urated monomexs used maY be any monomers whi c~h ar,ter into copolyme~rizati.on th the ~ ~'~' wi ' ;;:
' vinyl ethers of ' tile ~eiacta.l LVrtimlct. Ex.am~les of .
.;.
. suitable monom~.rs are acrylates or rnethacrylatejs, such as acrylic acid, teri=-b~.tyl metha~Ly~.a,te v1: ~t i utdthy=
methacry.late, ~I-yrene, vinyl chloxf.de, vinyl .~thers, ' ' acrylamic~es, ;'' acxylonitriles, ulrrLis (e~Hylraue, ~.
prnpyl Pn~a, htyJ.enQ or isobutylene? ,allyl coajpounds, ' . , ,.
vinyl lseatono9, vinyl a4e'L:ic: acid, ~ vinyl ';.
dL~~.ate or ~
vinyl esters, in pari-.i ~u 1 err, for, examrle, ''' ~ rnothy7. a .
methacry__atc, ethyl methacrylate, butyl methauiyldl.c, lerL-vu~wl methacrylate. methyl . ~r.rylatP, ; ' ethyl .
3O a~ry:~at~, butyl acrylatc, tort-butyl. acrylate;, tent-~ v butylauiiixruetxiyl esters, l-diethylamimnai-hy7.
; !:
mathac,ryl.ata, 2-diethylaminaothy~., vinyl ether, ' .
N 3 ~dietlaylcmimu~L~,pylmethaCrylamide, : 3-mPthac~,'ry~.oyl-i . is n . y ;;
i 1 ~ . ~ 1.
' . ii ' i i . ..
08/02 G~ U8: 2a FA% EGUSSA MARL, IPM ~-- CA FETHERSTON , t~
CA 02383030 2002-02-21 , ..
.. . : i - 5 _ '.
.;
v aminopr~~py1 trimethylammonium chloride, , 2-iacth8cryloy:l-v oxycthyltrimetl~yl~rrtnonium chloride , ~r 2-moth~cryloyl-, , oxyethy.ltr~mPthylammonium mcthoaulf~t'Le.
. ' ~ :
:
. 3 i .
Tt~c: alj phatir.~n i.y ur~saturatod monomers are pz~eLe.cwbly '. acrylic acid compounds ut~ taethaCrylic acid cc~mprnmd~i, dtiti Lhr: vinyl ethers of the general fortn3ula are - preferably 3-aminopropyl vytiyl ether. ~ ;t~
.
The nov~al antimicrobial copolyuel~ mdy be obt3lned . by ;
CopolymE~rizirig vi nyl ethers of the general fordnula, in i ,.
particul ar 3-amznoprvpyl vinyl c~l.rier.s ~ with one ! or mote aliphatical7 y nsaturated 'monomers . ' The polymc~ization ~;
io uocfully a free-r~t~lic;al ~~lytuerization using; a free- .
1.5 radical iniLiat~r or. inducod by radiation. ;Typical it . >:
.
.
procedures are deacriLed lrr Llte examples_ ~ "-.
' , .
The novE~l antimicrobial copolyxttera my~ ~tl3u ".
Lrr ~.bl.dlLleSi ';
by copolymerizing vi ny1 ethers of the gQneral :;'.
,formula, ' ;.
in particular 3-umir~,vpropyl vinyl ether witri t lCd~L
aj one alil'~hatiCal.l y on~aturated monomer on a substrate. .;
''"
Thus giwcc a physisorbad casting ofv thd aritlmlcwuk~idl '1~
' ' copolymer on the substrate.
f
2~ Suitable substrate materials are tssp~~ia L.Ly i ~ny~ of thp ~
' polyxti~ri~;. plaatico, r~uch as polyuret,hanes, pol~amidea,. H
..
pulyesl.e~w or palyethers, polyeth~r block i amides,.
not ystyr~~ne, polyvinyl chloride, pol:ycarbon3toci, poly- ,i t . vigatm~i.L~xanes, polyolefins. polysL~ltonPS, ' ' .
~(1 ;
~ ..
rolyisor.=anQ, polychloroprono, poly~ctrafluoro~thylene (PTFE)~ c~r ccri're5pcndinQ copolymers tlr hlPnd~, i~
~r a1 ~rz ~
r~
naturall~T occurring or ~ynthotic ,rubb~ra, kith j~~
or , .
withrrut tddidl.lon-sensitive groups. The hovel iprocess may also bQ used on the Eurfacoa of objccto tuufde r front 35 metal, from glass ut .Ct;'Ultl WUUd and E surZace-CO~ted ' or. ' otherwism Coated wii'h pl2stic. ' . v .;
..
n ..
. ~ ' 1 :
i : if ' t i , ~ , ' s ~ '.
. i i ' , .' ~ if .
;:~2 FR 08'30 FAX EGUSSA ~ARL.IPM ~-a CA FE~.'EERSTON .;
QS/0, 2 ~trJOf~i~
! CA 02383030 2002-02-21 ' '' .
, .i ' . - 6 i a:
In ar~o'._hor embodiment of tlw present invention the ; '' copolymers iudy be prepared by a graft polymeri~atior~ of ,y!
.
a ~nhRt~~ate with vinyl ethrsrs of the c~e~neral Io~mula ;I
.
. , ' ..;
, . . . ;
; . ;.
. v.
I ' a o . . i .n : '.., I v i O R' N . ' ' ,.
. . . ; .: .
:
' ..
' . ~s :.
~ ; a a J
...J
i ' '' :
where Rl is n branched or ullL.c:aiic:hed hyd~'oearbon ., radical having from 1 t~ 5 rsrhoxi atoms,. zr~d '.
R' and R~ arc H or a branched or unbramch~a v l~ycirocarbon radical having tram 1 ~hn 5 r_.ar?ao.n w ' atoms, where R' and R~ maj~ be idex~,t~cal or ~ "
' ' ' i di~f~1:~111., 'G
I
t.
in pazti~ular with 3-aminopropyl vi.x~,y7, ether, and witk~
, at leas ~: one aliphatically unsaturated mono~ln~r. The ;
lydIL111t~ rJr the substrate allows covalent linlking n:~
, I
the antimicrobial copolymer to ~ tho mulwtratc. . '' ! Substrat~ss wlilc:h may be used axe any p~lymeric '' ' m~tari a1 , such as the plastiCS mr~ntior~ed above. ~ ~. '' '. , a ~
a y ~
Eri or i-.~'. the graft copolymerization~, th~ surfaces oi: ~i ~ ,a ~
' .
the substrate may Le a~Livdlevl Ly d Ydtlel.y ~r tuel_Zmds.
~lny :,I ~nnard method for activating polymer surta~ces may ~
~SUk~SI.LwLc~ array be ~ ~~~
be used here, for ~sxduyle l.tm .
, ~
activa,tRc9 pricir to the graft. pol~mariaa.tion ; by LT~~
w radiation, plasma tZee~.tlu~uL, c:vtwtm~ Lreal.ment,i fl8me e Lreatmenl:, ozoni ~~ta.on, electrical discharge or . .
j ~y-radiat:~ ors. The surfaces aie us~sPully LL~eec~ in 'advancE
:.
iu in a known manner trom r~i I ~, fatc or'. other ' . :
,:
~f1 , rontamin<<tion, urging a lvcnt .
oo ' , .
.
<
' Thr=a subs =rates may bo ~ activated u3irig W radia,~:ion :;
ii:.
' the wav~:l~llyl.li range Irom 17U r.o 4tl.V nm, pre~terably . . . . .~
~i ~ , 1:~
a . . ' i~
.
.
i . , . . . .
48/42 02 D890 FAg EGUSSA MARL, IPM ~~~ CA FETHERSTON, ~, FR I~010 .
' ' ' . - 7 _ ~ .
i ' . . ; ' ' : ,;
from 17U fin 750 nm. An example o a suitable ~adiatic~n ~, ' source is a NoLlellqht ~ W' nxcam~r arraratus frcym ~~
I3ERAFUS. Hanau, Germany. However, mercury vapbr lamps arc also suitaLl~ ,Cor substrate artiv~tir~n as; long .m .:
.
they emit m.~bstantial proportions of raaia~ior~ in the abov'cmcaltipned ranye5 . The exposure time i s c~Qnarally ;
LtOln 0 . 1 Secnn~l~ to 20 miniateo, ; pxcierab7.y : frultt ~r 1 .
, second ~t:o 10 minutes .
~ ., .
; ~ .7 ' 10 Th~ acta.vation of the substrd.te wi~tl. W radiation prior ;..
"j ~
;
i ;
'CO the ~~ratt polymc~rxzation max alEO be done ~'ir:,g an additional photo'em5l~lzer. For this,! thR ' ' phntn~IRri tlZer, such as bonxophentino, is applied tc'r 'j the aub..strate suzLac:e and irradiated. ~ mercury vapor lamp may again be used her~, with;exposure ~imco of a from 0. 7 second to 20 rn i.~~uLes, preferabJ.y from 1 second ' j ~ S
Lo 10 minutes.
' . ~ .: ;:
i ' .'r r, ..
ACCOrdir_g to the j nvA"ti em, the acUivation may also ba i .
' ..
. achieved by plu3ma treatment using an RF OR lu.~c:LUWdVr3 '.' plasma (Hexagon, TPchnics Plasma,; 85551 Ki~CChhoim, Germany) in sir, nitragen or ttZgull a'~luubpliei'~5. Tht~ i;
h exposure times are g~nar~lly from 7 seconds; to 30 1 i S
minuteo, prefexa.bly from ~ secvlzcl.s to 10 rnilluhe5. TtlL
energy supplied in. the na~P , of I ~h~ratory deviices i:>
.
' <..
from 100 to 50U W, preerably from 20:0 to 300 W. ~ ' j ' j . ':.!
Coxona cl~vic~s (SOFT11L, Hamburg, Ce~many)' may also be:
used for activation. 'fhe exposure times j.n t-hri:~ c:aaP ', . i.
are generally from 1 to 10 minutc~,~preferablyfxom 1 ;
t0 GO sCV011C1S .
' ~ ' ' :;I
. s,N
j.
Activati:am Ly electrical discharge,; electron beam or. . e~
y-radiation (e. g. from a cobalt 60 ~~ouroe), aid alas O~Oriiaat_o~z, allows short exposure : times, Q~ynerall~
..;
from U.l i-~ HO seconds.
.. ~, 5ubstr.atca surf~~as may also be activated by flame ;
, ' treatment:. Suitable devices, ~.r~ ~ra~ Li~;uldr~ Lhosewith ~' a ~
j!
.. ,. :"
i ~ ~ .. : 4 ; 'i , ' ~ . 1 j ' ' ' 7 08/42 42 48 94 FAZ EGUSSA MARL, IPM ~~- GA FETHERSTON I~ 411 FR :c CA 02383030 2002-02-21 , ~ ;
l ' - 8 - . . ; .
tF
barrier fl.ama front, can road.ily be constzuc;l.ec(. or, .a, for ' examplo, purchasr~a from AFLUU'fla;C, 71797 l~Ic~i~sheiia, air ~~
Germany. 'They may ba oporatcd using hycl.zuc:ct~'bonS ox~ '!' ' , hydrogosz an comLuS l"iUrl gas . In ' a I I cases; it ~ s :
ttecessa::_y cc, avoid dam3gc to :the suLsl.~'ate by ' overhcai.in '. '' g, arid i,ttl5 can readily : h~ ansuror~ if the ;:
surface of thR suhstrat~ facing aG,,ray fxom tl~e Llatne ' treatmcr~t side is lm intimate contact wi 1'.h ~ cooled '. v1 ', tnetal surface. Activation by flaino treatx~ent is ~i ther~for.~e rcatricted to ieldLlvely thin, sh~Pr-like .
l . r~
substrai.es. 'fhp ax~nsure timos arQ g~narally from 0. Z ';
' , , . _:
second -.:0 1 minute, prefeid.Lly rt'om; 0.5 to 2 Seconds.
;, The flames arP exclusively nonluminouc, t~.nd the . n dictancc3 between tl~e ~uLSLi'aLe sur~aees and tl~e ourpr side o1 the f=lame front are f>"om 0.2 t~ 5 cm, preferably from 0.5 Lo 2 cm. : ' . ;P
l ;
The subEvtrate aurfacea act~.vdtwl iii Llli~ wdy itt'~ coated by kno4~m method, such as digp;ing, spraying or l . 20 spreading, with vinyl ethers of the genezal l Lut:tuula ~
( compone n;C 11 , in pa r1- l c-." 1 a r wi th 3-aminopropyll uinyl '' ether, a.nd with one ox more aliphatically uns~tuxdlec~ '' . ?~;
.
monomexs . ( component I I ) , l n ~~ 1 t l nn l f_ r~esired _ ' Sol~trent~ which haves proven useful are wai~ez dttd ~ '3 '; z5 water/eL:Zanol mixtures, ht- nth~r soavents may iaiso be ' , c:dp~Lle v:: '' ~~
' usod ao long as they are su.fficaently :.
- f disso7 vi;l~1 the monomers anal qi va c~~~ci wati-i n7 '., of the " l!
. ~'i substxat~~ surfaces. SolutioriO ~~ith monomer contents of ~
.
' fJ
Lt'Ulll 1 to 10~ by weight, for ex~mplP 3hc~nt; 5~ 17y ' ~0 weight, have proven successful .in practice and l.
~
' ~
generall:~ give, .itt ~ single Dass, : coherent cinai-i ng4 ,:
which covor the substrato surface anld have thi~knesses ::.
. .,.
' whi eh. eau be moz~ Ll~dn 0.1 elm. ~ ~'.
'l 35 The graft copuly~ueri~ation or the monomers applied t~ _;.
ttie activatarl surfaces xnay usefully be initiated by . ~y .
radiatiorr ' in the ~lmi'L-wave segment of the ;visible ~ it~
range or in thp loncJ-wave segment of the W r~ngc of ~ l electrommgnetic radiatiuii. Fut ext!lnple, the radiatic'm ; l '; a ~
. , , , ~ ,;
:; y:.
!~
48/42 42 48x31 FAZ EGUSSA MARL,IPM ~~r CA FETaERSTON ~fJQl2 FR
r . .:
,. r _ 9 - ~ .. ; ;:
. , :t . ,, . from a TTV excim~r of wavelengths fZuiu 250 to 500 lun, i pxcfera~ly fium 290 t.o ~~U nm, .is very suitablQ.
Mercury vRror lamps aro alao ,~uitaLile here ash long c3S j~
they helve suLal.dcitial propori:nq of ra.diatiox~ in the ' 5, abnvPmRntipned rangao. The exposure tiiues are generally '. from 10 secoiias Lo 30 mi~rluCes. preferably from; 2 to 15 ~~
' minur.es . ~ .
.L
1.
, it i . i ;:
A Qrait r~polyzncrizaLio~n of the noveh Cjpmo110Tetrri'
' polyxti~ri~;. plaatico, r~uch as polyuret,hanes, pol~amidea,. H
..
pulyesl.e~w or palyethers, polyeth~r block i amides,.
not ystyr~~ne, polyvinyl chloride, pol:ycarbon3toci, poly- ,i t . vigatm~i.L~xanes, polyolefins. polysL~ltonPS, ' ' .
~(1 ;
~ ..
rolyisor.=anQ, polychloroprono, poly~ctrafluoro~thylene (PTFE)~ c~r ccri're5pcndinQ copolymers tlr hlPnd~, i~
~r a1 ~rz ~
r~
naturall~T occurring or ~ynthotic ,rubb~ra, kith j~~
or , .
withrrut tddidl.lon-sensitive groups. The hovel iprocess may also bQ used on the Eurfacoa of objccto tuufde r front 35 metal, from glass ut .Ct;'Ultl WUUd and E surZace-CO~ted ' or. ' otherwism Coated wii'h pl2stic. ' . v .;
..
n ..
. ~ ' 1 :
i : if ' t i , ~ , ' s ~ '.
. i i ' , .' ~ if .
;:~2 FR 08'30 FAX EGUSSA ~ARL.IPM ~-a CA FE~.'EERSTON .;
QS/0, 2 ~trJOf~i~
! CA 02383030 2002-02-21 ' '' .
, .i ' . - 6 i a:
In ar~o'._hor embodiment of tlw present invention the ; '' copolymers iudy be prepared by a graft polymeri~atior~ of ,y!
.
a ~nhRt~~ate with vinyl ethrsrs of the c~e~neral Io~mula ;I
.
. , ' ..;
, . . . ;
; . ;.
. v.
I ' a o . . i .n : '.., I v i O R' N . ' ' ,.
. . . ; .: .
:
' ..
' . ~s :.
~ ; a a J
...J
i ' '' :
where Rl is n branched or ullL.c:aiic:hed hyd~'oearbon ., radical having from 1 t~ 5 rsrhoxi atoms,. zr~d '.
R' and R~ arc H or a branched or unbramch~a v l~ycirocarbon radical having tram 1 ~hn 5 r_.ar?ao.n w ' atoms, where R' and R~ maj~ be idex~,t~cal or ~ "
' ' ' i di~f~1:~111., 'G
I
t.
in pazti~ular with 3-aminopropyl vi.x~,y7, ether, and witk~
, at leas ~: one aliphatically unsaturated mono~ln~r. The ;
lydIL111t~ rJr the substrate allows covalent linlking n:~
, I
the antimicrobial copolymer to ~ tho mulwtratc. . '' ! Substrat~ss wlilc:h may be used axe any p~lymeric '' ' m~tari a1 , such as the plastiCS mr~ntior~ed above. ~ ~. '' '. , a ~
a y ~
Eri or i-.~'. the graft copolymerization~, th~ surfaces oi: ~i ~ ,a ~
' .
the substrate may Le a~Livdlevl Ly d Ydtlel.y ~r tuel_Zmds.
~lny :,I ~nnard method for activating polymer surta~ces may ~
~SUk~SI.LwLc~ array be ~ ~~~
be used here, for ~sxduyle l.tm .
, ~
activa,tRc9 pricir to the graft. pol~mariaa.tion ; by LT~~
w radiation, plasma tZee~.tlu~uL, c:vtwtm~ Lreal.ment,i fl8me e Lreatmenl:, ozoni ~~ta.on, electrical discharge or . .
j ~y-radiat:~ ors. The surfaces aie us~sPully LL~eec~ in 'advancE
:.
iu in a known manner trom r~i I ~, fatc or'. other ' . :
,:
~f1 , rontamin<<tion, urging a lvcnt .
oo ' , .
.
<
' Thr=a subs =rates may bo ~ activated u3irig W radia,~:ion :;
ii:.
' the wav~:l~llyl.li range Irom 17U r.o 4tl.V nm, pre~terably . . . . .~
~i ~ , 1:~
a . . ' i~
.
.
i . , . . . .
48/42 02 D890 FAg EGUSSA MARL, IPM ~~~ CA FETHERSTON, ~, FR I~010 .
' ' ' . - 7 _ ~ .
i ' . . ; ' ' : ,;
from 17U fin 750 nm. An example o a suitable ~adiatic~n ~, ' source is a NoLlellqht ~ W' nxcam~r arraratus frcym ~~
I3ERAFUS. Hanau, Germany. However, mercury vapbr lamps arc also suitaLl~ ,Cor substrate artiv~tir~n as; long .m .:
.
they emit m.~bstantial proportions of raaia~ior~ in the abov'cmcaltipned ranye5 . The exposure time i s c~Qnarally ;
LtOln 0 . 1 Secnn~l~ to 20 miniateo, ; pxcierab7.y : frultt ~r 1 .
, second ~t:o 10 minutes .
~ ., .
; ~ .7 ' 10 Th~ acta.vation of the substrd.te wi~tl. W radiation prior ;..
"j ~
;
i ;
'CO the ~~ratt polymc~rxzation max alEO be done ~'ir:,g an additional photo'em5l~lzer. For this,! thR ' ' phntn~IRri tlZer, such as bonxophentino, is applied tc'r 'j the aub..strate suzLac:e and irradiated. ~ mercury vapor lamp may again be used her~, with;exposure ~imco of a from 0. 7 second to 20 rn i.~~uLes, preferabJ.y from 1 second ' j ~ S
Lo 10 minutes.
' . ~ .: ;:
i ' .'r r, ..
ACCOrdir_g to the j nvA"ti em, the acUivation may also ba i .
' ..
. achieved by plu3ma treatment using an RF OR lu.~c:LUWdVr3 '.' plasma (Hexagon, TPchnics Plasma,; 85551 Ki~CChhoim, Germany) in sir, nitragen or ttZgull a'~luubpliei'~5. Tht~ i;
h exposure times are g~nar~lly from 7 seconds; to 30 1 i S
minuteo, prefexa.bly from ~ secvlzcl.s to 10 rnilluhe5. TtlL
energy supplied in. the na~P , of I ~h~ratory deviices i:>
.
' <..
from 100 to 50U W, preerably from 20:0 to 300 W. ~ ' j ' j . ':.!
Coxona cl~vic~s (SOFT11L, Hamburg, Ce~many)' may also be:
used for activation. 'fhe exposure times j.n t-hri:~ c:aaP ', . i.
are generally from 1 to 10 minutc~,~preferablyfxom 1 ;
t0 GO sCV011C1S .
' ~ ' ' :;I
. s,N
j.
Activati:am Ly electrical discharge,; electron beam or. . e~
y-radiation (e. g. from a cobalt 60 ~~ouroe), aid alas O~Oriiaat_o~z, allows short exposure : times, Q~ynerall~
..;
from U.l i-~ HO seconds.
.. ~, 5ubstr.atca surf~~as may also be activated by flame ;
, ' treatment:. Suitable devices, ~.r~ ~ra~ Li~;uldr~ Lhosewith ~' a ~
j!
.. ,. :"
i ~ ~ .. : 4 ; 'i , ' ~ . 1 j ' ' ' 7 08/42 42 48 94 FAZ EGUSSA MARL, IPM ~~- GA FETHERSTON I~ 411 FR :c CA 02383030 2002-02-21 , ~ ;
l ' - 8 - . . ; .
tF
barrier fl.ama front, can road.ily be constzuc;l.ec(. or, .a, for ' examplo, purchasr~a from AFLUU'fla;C, 71797 l~Ic~i~sheiia, air ~~
Germany. 'They may ba oporatcd using hycl.zuc:ct~'bonS ox~ '!' ' , hydrogosz an comLuS l"iUrl gas . In ' a I I cases; it ~ s :
ttecessa::_y cc, avoid dam3gc to :the suLsl.~'ate by ' overhcai.in '. '' g, arid i,ttl5 can readily : h~ ansuror~ if the ;:
surface of thR suhstrat~ facing aG,,ray fxom tl~e Llatne ' treatmcr~t side is lm intimate contact wi 1'.h ~ cooled '. v1 ', tnetal surface. Activation by flaino treatx~ent is ~i ther~for.~e rcatricted to ieldLlvely thin, sh~Pr-like .
l . r~
substrai.es. 'fhp ax~nsure timos arQ g~narally from 0. Z ';
' , , . _:
second -.:0 1 minute, prefeid.Lly rt'om; 0.5 to 2 Seconds.
;, The flames arP exclusively nonluminouc, t~.nd the . n dictancc3 between tl~e ~uLSLi'aLe sur~aees and tl~e ourpr side o1 the f=lame front are f>"om 0.2 t~ 5 cm, preferably from 0.5 Lo 2 cm. : ' . ;P
l ;
The subEvtrate aurfacea act~.vdtwl iii Llli~ wdy itt'~ coated by kno4~m method, such as digp;ing, spraying or l . 20 spreading, with vinyl ethers of the genezal l Lut:tuula ~
( compone n;C 11 , in pa r1- l c-." 1 a r wi th 3-aminopropyll uinyl '' ether, a.nd with one ox more aliphatically uns~tuxdlec~ '' . ?~;
.
monomexs . ( component I I ) , l n ~~ 1 t l nn l f_ r~esired _ ' Sol~trent~ which haves proven useful are wai~ez dttd ~ '3 '; z5 water/eL:Zanol mixtures, ht- nth~r soavents may iaiso be ' , c:dp~Lle v:: '' ~~
' usod ao long as they are su.fficaently :.
- f disso7 vi;l~1 the monomers anal qi va c~~~ci wati-i n7 '., of the " l!
. ~'i substxat~~ surfaces. SolutioriO ~~ith monomer contents of ~
.
' fJ
Lt'Ulll 1 to 10~ by weight, for ex~mplP 3hc~nt; 5~ 17y ' ~0 weight, have proven successful .in practice and l.
~
' ~
generall:~ give, .itt ~ single Dass, : coherent cinai-i ng4 ,:
which covor the substrato surface anld have thi~knesses ::.
. .,.
' whi eh. eau be moz~ Ll~dn 0.1 elm. ~ ~'.
'l 35 The graft copuly~ueri~ation or the monomers applied t~ _;.
ttie activatarl surfaces xnay usefully be initiated by . ~y .
radiatiorr ' in the ~lmi'L-wave segment of the ;visible ~ it~
range or in thp loncJ-wave segment of the W r~ngc of ~ l electrommgnetic radiatiuii. Fut ext!lnple, the radiatic'm ; l '; a ~
. , , , ~ ,;
:; y:.
!~
48/42 42 48x31 FAZ EGUSSA MARL,IPM ~~r CA FETaERSTON ~fJQl2 FR
r . .:
,. r _ 9 - ~ .. ; ;:
. , :t . ,, . from a TTV excim~r of wavelengths fZuiu 250 to 500 lun, i pxcfera~ly fium 290 t.o ~~U nm, .is very suitablQ.
Mercury vRror lamps aro alao ,~uitaLile here ash long c3S j~
they helve suLal.dcitial propori:nq of ra.diatiox~ in the ' 5, abnvPmRntipned rangao. The exposure tiiues are generally '. from 10 secoiias Lo 30 mi~rluCes. preferably from; 2 to 15 ~~
' minur.es . ~ .
.L
1.
, it i . i ;:
A Qrait r~polyzncrizaLio~n of the noveh Cjpmo110Tetrri'
3 compoun~:lo can also Le dc:liieved by a prCrPSS rijascrib'ed;;
:
in rtlrn).man Patent Application 0. 972; 512 and baled o~~
a ~.
graft pc.~lymerizativci or monomer molecules and ihii-.i ai-nr . s.
ma 1 Rr. i P s . incorporated by owe 11 ing . The mononEer used for the ~wallirm may be component .~1. j ~.
' 15 . ' ' Even wi~.hout grafting onto a substrate surtar.A, the novel alntimirrobial copolymers o1' vinyl cthcr~! of the , . ~ general formula (c:muputmnL I) , 'in parLlCl~lar _3-- , amin~prr.pyl vinyl ether with at least. ono aliph~tically y ;
. 20 unt;atur~ted monorcver (cmu~ruueuL~ II) show microbi.~~.dal i or ~ ..
.: ;
antimic:.rohi~l hahaviour_ Another embodiment ~oi' the :
., prcocnt invention w~txsi~ L,~ iii e:ci.i'L'yiny o~.tt the ::
copOlymefiZatlon nt ~nmponentR T andII on a sub~5trate. ~
. 2 :, . ~ ; . I
Z5 The componpnfi~ may be in~ solution when applied to thv ;
subatrat~s. Examples uL sui~aT~lc~ solvents are; water, ~
ethanol. methannl , methyl ethyl ketcine, diethyl; ath~r, ' dioxane, hcxax~c, heptane, benzene, toluene, chl~Lofumu, , diChloro~aethane, te~i-.r~rly~r~for~n and acetonitr~lQ_ Ii:
;
30 i~, also possible to use component 'II as solvent fog: .
; i couyu=len , I . , .
.;, , . ; }~
i :'i The muv~~1 arrLimicxobial copolymers ' may also kip mach e;' . ,1!
.. , ' directly, i.~. not by polymerizing the components on << > t~
suL~t~aLF: bud as an antimicrobial ; coati nQ_ ~~ni tah'.l~r~!~
c~.c,at'in~ m4thods are application of 'the copoly~nera ire ~ iP
SCtlut1011 uZ d5,d melt.
, = i .
j . . : . ', ' ' o:
i . I
. . . . .
' ' "
' ~r : ' , i , . ~ i i~
i 1.1 ' .. :N
' ' ' i . .
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t l!
o2 FR 48' 31 FAa EGUSSA MARL. IPM ~~- C.A FETaERSTON. , Q8/0 2 , IQ
n19 CA 02383030 2002-02-21 . ~i~
y ~
ji 1 ~ - . . ~, . . , ; . i Thp solution of the novel polymeiw may be ap~liec~ I-n :;
the aul:~atrate5 by dipping, ~sprayin.g or pairsti.ng, for '..
examp'i a . . : ~. _' ;
'' ' :
~ s;
~ ~ :..
, ,..
. 5 , ~r i >= the novel polymers are u~ea~ directly I on the ~
,.
y substraU:e ~5urfaee without: c~rafting,v conv~nt~.on~l free ;
j ~i r~riiral initiators may be added. ;
y, ' t ~ ;
Exampl R::: of initiator , ;
which . may' be us~:~l . iss the !: t .
' ' 10 preparation of LW novel. copol ymara ' arR~, inter alts, a~nni trles, alkyl pcroxide3, hy~lroperoxirla~, dc:yl , t peroxides, pezuxuY.etones. pere3ters~ peroxorarhnnates, ~~
t o :r pProxodisulfate, peraulfatc and ainy of the usual photoinitial.ut'S, such as arPl~ophRnr7na~, a- , ; t 1.5 hyc~rnxy~-etonvs, ,dimethylkctalo t~rsd ~ benzophonone .
The ~' ,k ' polymeL~ cal.lon may also be 1rii'tiate~l. thPrm~1 1ynr, .'.' ~as .
.
a 1 re2d,y stated, by electromzgnctic 'radiation, auC~x a3 .
W light or y-~d.raldLiOn. .
t ~ ~ is 20 The novr:l ruutimic:robial polymers mar also be ;used as , ~nmrnnents~ for formulating inky, p3into o~ other surface coatings. , ' t ;~~
' ; ; .w .
:
..
Use of t:~c modified polymetr auL~L~~al.~s .";
G5 The prp:;sni-. invention also provides the use ~ of the ', 'ui ;, novel anrimicrubidl pulymeiw l.u produce antimic~obially aotiva l~rnc~,.,ots, end the products por so which are v!
. :
.
produced in this way. Tlse pLUauul.5 rosy C;UlIl~1'luC ipUlylll.el'.
~ t;
S11hS1'.ratms modified according to ;the invcntivn on ' 30 pe dLe ,pL~r~rably a '.
conaiot of these. Products of tlui~ ~y , based ors po7.y~mi ~fPS, rolyurathanes; polyether block t amidos, polyc3t~ramidea or -imidea, PVC, poly~7.afim, ~ is s', Sillcone;a, polysiloxanta. polymethacrylatP or; p~ly-t;
t~rQphthrWatoa which are surface--modifiied uaini~ novel ;
., 35 . . ;c pulysuers.. . ' ~ .
. .
. ~ ;:
t :k Exd.xuFsles ~of antimicxobially active ; pr~cinri-~ cif this type axo ix~, particular mnchine parts rod food pltJlaiD~llLf~, components ~.n a 1 r-rnnp tinning systems, .!;
' t .lt ~. ' a , 1 . . t -:
~ . ' I
:
OB/02 02 FR o8 ~ 32 FAg ErUSSA MARL, IPM ~~~ CA FETRSTAN , IQ
pid ., CA 02383030 2002-02-21 . ~;rj o ;:
' ' ~i - 11 - , :.
rooting, items for bathroom and tuilc~L use,! kitchon items, components ur sanitary cquip~n~nt, comp. r~ents of CaCreS cr hOlIRRS for animale, recreational pZUC~ uc:ls for childr~;z, components u.C wdLer systems. rood p~ ckaginc3, Oj7~Id(.U:_' units (roLich pan~ls) of device's, and l conLac:L
~. .
r lenses . ~ ; s :, .
;~
fho novol cvpalymers ur Graft copolymers ~ may I tip LlSQd anywher~:~ where imrortance is placed on Surfaces YVl.th '..
! 10 release pxop~srties or suz,Cdc:eS which, are 'very ffPP tram ', baCteri, i.P_ mi.crobicidal. Fr..amplo~s of opplic~.tion of the nv acl ~ CQpOl~lmGl ~ uL' y.~~att ' polymers fare in ' partieu7 ar ~ snrt'ace coatings, protective pai~2tt~ and v other ec:atinga in the fulluwiiiy 5ec:l.t~r's : ~ , a ' 15 ' ' ' Y
il~
- Marine: Boat hulls, c~u~k5, . buoYS. ctrillinq a pl.2tforms, h~7 7 ast water tanks v rr ..
' - con ,truction: Rvofinq, Laseumu~5, walls. facades.
a greenhomP9, Burr protection, g~rdan fencing, wood 20 protection ' 5anlLary: Pnh1 l c conveniences, ' bathrootns, ~ shower .
' cur trrina, toilet items, swin.uuit~y Yuul, . ~dunar l -~oiztinc_i', sealing compounds ~r .
, ~ tchen, Mz~c:hiriea l - Reqwisitoa foe daily l~,fe:
l 25 kl~ ;hen items. sponge pads, recrear.iona.L pr~dnrt:a ..:
for children, food packaging,; milk pro~aasingr '.
. ' ' ' drl:~kinc~ water systems, cosme_tir.,.s ' ; .
, ion - Machine party: llir-Conditioning systems , l ; ;, exchangers, process w~tPr, ~c~~ i%iT'-~)C7W?1'PC,i . units, r . l .
' 30 hew:. exchangers, bioreactora, membranes : ;~,v I l SJ
= Mea.ic:dl technology: t:nni-.arr :1 pngaa, rii aper, s, . : ;.
memi~raner, implants ' .' .>>
- cun;ju~u~r articles: l~utomobile seats, Clothing 3 (souks,~ sports clothing) , hospi'i~al cquipmcr>!L, door. a !
:
: .:
w 35 hant~Zca, teld~rnu~xe tmc~dbe~s, public conveyances. ,r l anin.Wl caQA~, cash registers, wall;to-wall.
, ' carpets, , wallpal'rr.c s . .
. . .. fl.
. ~
.
, ".a . ' , ' . .;r l .
' . ~ .. ..
t P
:..
. . x ' ' . . . ..
. ..
. ~ ~ . . l:
'.
Os/02 n2 48.32 FAg ErUSSA MARL, IPM . --~~ CA FETHERSTON ~~, FR td~i5 :
.
CA 02383030 2002-02-21 . ':
. . ' : " ~~;
- 1~ - ..
. .; ..
; . . . ~~
.
Z~he rJrPS~.lTtt ihVaritl.Oh al:lO provid~ss~ ' rOr the use of thc~
;:
novel ;?olymcr ~ubstxates, whngA surfaces h~vo bees 'i modi.rie~x ming novel polymers 'vr ~JZUC:e55~fS, ' for ' ' producing hygicu~ products Or . i tams in medical ..:
~
~tchnology. ~nhat which has been said above. uNmeerning preferrsad materials ap~alies Correspondingly_ ~p ~Rxampl~es .
yr tiyq:. ene prodnrt~ of this type: arc toothSbrushc;:, ,.
'toilot ocats, 'combs dmci packaging mateZials. iS
'the term "
hYqiene item alga includes othwr ob~octo which inay conic into contact With a latue mut~~er of. peopl p, gt~rh as ;
' telephor,P handsets, stair. railo, door h~ndlcs; ;;
Willl'~VW ,~
catches, and graL S LL'a[J5 and grab ' handles irk ph1 i c i convayai:ra~_ Exssnples of item.a in :medical f':
tcGhnology a:
arc catheters, tuLiy, ~.)L'ULecLlve or backing '.
films encl. ~
a ;:
also surgical in~tr~.~ments . ' . ' r ;(:
';
' . ~, i:
s.
,, The tolloWirig examples are given in, order to ~.escribo the pror.~cnt inPentian in greatcl ~lel.d.il, r ~ul. ~c~,re not ~ ..
intended to limit its scone as set~out in the , patent 2 0 clai~na .
.
ai ~ , ..
'.
:.a $xat~plc 1: ' ' s' ' ; ~.
' 6 q Of 3-aminopropyl viny I ~ rf'hPr ' (A1 ~iri rh ) , ; E'., g of ~~
methyl aiotho.crylate (Aldzich) and G0; ml of "!' cth~liol aie ' ;, charged Lo a three-neckPr! t I ask ~n~i h~ai-aci ~o ~S"n ~n . under a ctreain of argon. , . 0.15 [g oz" , ':
.
.
acobisis:~butyronitrile dissolved. iri 4 ml oir :
ai~hyl ' n . ~ ~
.
z~nethyl .cetoiie is then alowly added dropwisd, ':
with i ~
:
stirring. The mixture is t'lP~3fiPf~ 1-W '7;17(".
~h~i ~ati~.r.rer_l at ,:
this temperature fox 72 h. After cxpiry of this ~"~
time : ' the r~ae; ~ium tulxture is stirrP~I i nfin ~ iJ
. ~i I nt rl~si onized ' T
water, whcreu vn the .' ':' p polymeric pro~3uct precipitates.
I !4 Rfter tille.c~.inq oft the product, Lhc filter ~:akp i washed orith 100 ml of dc~.or~i~cd wu~Ler to rembvc '"
an~r 'y ' 35 monomer resirlud5 5L111 present. The product ~.s them ~i dried i,u vacuo fir ~a hours at 50C.
.
t ,:
' v yh ' ~ :1.
, .
.
i . ' i . y .
. . I
~
i 1 . . . :h :i)' i . ; i d":
I ,i"
' ' i ' 48./42 48' 92 FAY EGUSSA MARL, IPM ~~~ fA FETHERSTON, ; Id , ., CA 02383030 2002-02-21 I'' ' . . a~:
_ 13 . . . : <:
, ~ ..
E~a i .
0 . O5 g ~f ~xie product trim Example I is Ehakcn in 20 zal ~f a tort micrvbicl suspec~slon , or 5taph~.l nrr,rcvs aureus. ALLer a contact- time of 15 mi'nute~, '..:
i1 ml of "
rrte tra.=:t microbial auapensium 15. removed, , land i:ha ~' , number of microbes iri the 1-.Rqt- mixature is de~eizaincc(.
iF
After Pxpiry of this time Ota~hylowuuus~ aureus ', ' microbes al'e 11U lonqer detectable. . . . ;):
~
,.
.
.
EXample 1b: , i , . ' U.()h r~ r.:~f the product from Example 1is shaken dim 20 ml ' i :
; ~
of a ta5l. microbial suspengi ~Ih of Pswhdomonas ya ' :
aerugincsa. After a contact time of ~i0 zuiiiul.e5, ~
' Z m1 of -tlw les ~ microbial suspPnsi nn i ~ ~ rPmwed, '.r end th~ ~~ :
:
, number c,f microbes in the teat mixture is det~rminea. :
a vi ,.
' After e~:pi.r:y of this' time ~Che numhPr nfi mi nrrjhes has rs~dtma~l from 10' to 10c . ' I
Exat~rls 2:
I . . it 6 g of 3-aminopiu,~yl vinyl ether. '(Aldrich). 6 g of .
hntyl mr:~thacrylat~ (Aldrich) and 60; ml of cthr~nol are iY
charged to a three-necked flask arid heated ~0 65t.:
under n stream of a~'yon. ~ 0. ~.5 ;g o:~
.
~s~obiaia~butyromiL~ile dissolved 11~ 4 ml o~ ;
ethyl ~ .
:
. ;
~5 methyl cpt~na is them slowly added dropwise, with _ !
'. a stirring. The mixtu.ce i5 tieaLed Lo 7:0"C and st~fred a1:
this tenpArarttra far 72 h_ After expiry of this time , the reaction mixturo is atirra~l iiitu X0.0 1 UL t~Erj.u111GCC~
water, mherPUprtn the polymeric prosiuct precipitates . , l~ftor f; ltering off the product, tIm filtez 'y (:eke i5 washed with 100 mi of cieionized water to r~mpv~ ' , any n4 monomer rc~idue9 still preseazt. This ~rLUCiu4~
is l.hen dried iz~ vacuo for d9 hnur~ ~t ~7Of._ : ' ;j;
:
., .: c s, ~
r ~ i 3u Ex~uupl~ .?a: . : a~.
1.
~ . 0.5 g o. th~ product from Exazuple 2, as shaken ~_:
i~a 20 m7. ~
of d l.e5l. microbial Suspension ~~f ~t-arhyLococcus j ~lSrpW . After a contact . time of 15 v minutes, ~w 1 ml of the test: mioiuLial Suspension is .:'removed, ~nh the r n 1' ~f I i h 't ' . i.
j i I
I . . 9 , j ~ ' , a . ~ ~;
08/02 02 08 93 FAY ErUSSA MARL, IPM -~~ CA FETHERSTON .~
FR I~
01~
CA 02383030 2002-02-21 :
' - 14 - ~ . . ;:
nLUribpr nfi microbes i.n tho test mixture i8 deLermin~cj, :
( I
lifter expiry of this time Staghylococeus; aureus , ' ';.
microbe. ara no longor detect~xble. . . :.
S Ex~Dle 2h i 0.05 ~ f the ~' ~ ' '' J p'rwduCt from l;xa~p.l p ? is shaken ;in ~0 ml ~
; ;;, I oI a 'test microbial cuvpcnsion of Pae~ut.~omonas acruginc~sa. Aft~aw a contact time of 'HO minutRS,' ..f X ml of :
the te~:L mirrc:,bial suspension i3 , removed, hand Lh.e 10. number r.~f microbes iu , the test m~xturP i a a;
. clPt~rmined. ~
~
v After eapiry of this ti.m9 the number of mi4rqbes has '..
1 ,.
; .. .
. reduced from 10' tc~ 20' . .
. , .i .
=i ' Ex~pl~ 3: ' , ~ ' i 15 . ..
6 g ~f :3-aminoproPyl vinyl ether (Aldrich) , G ~g of 2- ~
?c diethylamimuel.lAyl methacrylate (Ald~ich) anti ?'.
fl7 m1 of '' t.
.
. ;
ethano I are charged to s three-necked flaals and hee~t~3 ' to 65r: under a Stream of argon. 0.15; c~ ~r ~~ '"
a azobisisobutyrc,r,i trile dissolv~d iri 4 ml of ;r ethyl ~;
20 methyl ketone is then slowly aac~ea cWopwlse, with . stirring . '1'hR mi xtura is heated to 70C and =r . st~!rred at ;' ..:
f .
thi.o temperature fp3; 72 1~. ArLew eispiry of this time the reaction mixi,ur,e is stirr~d intvØ5 1 of d~ionized water, whereupon the pvly>.ueilu ~rvld.uct t~reci~itates.
.~
25 After tl.ltP.ri nc~ off tha product, the filtor fake washed ~,~ith 100 ml u.C deionized water to remove aii any ' ztloriomer resich~as still present _ The product is then _..
:;
r I
.. H
dried in vaCUO for 24 haura at ~0C. ' i ..
a :
' l::
, ' 30 Exa~mplc 3a: : " ~~I~
.. ' ;.;
0. OS 5~ v C the Droduca from h;xamp i P B .; ;;
s shaken ',in 20 m~. ;
of a test microbial suspen'ion ~of utaphyloco~:cuu j auteus. RrLer a Contact time of 15 mi.rn~tP:~, ~ m1 of i the t~sT: microbi.ul suapenaion is : removed, a~n ~l :~llr.
a 35 mulula~L~ u.t microbes iri the t:PSt mi xt~~rR y i ~ rlPt-~.'~rmined. ' pftar ex(~iry of this time the number of microbes ~~~
has , reduced frc:uu IO' to 10' . , n . . I
..
I :' II
.
' ~ 'A
. . ~ ~I
r i , n . .1 I
. :s ~ ~ .. .
08./p2 08' 33 FAZ EGLtSSA MARL, IPM i~~ CA FETBERSTON i~
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CA 02383030 2002-02-21 ' . - 15 - , ' ~ ':
Example jb: : ' ' .
:
0. 05 g of.: the pzuc~uct from bxamp I a .3 is shaken din 20 ml a , :;
of a tact microbial suspension ur Ps~udomohaS
aorug~.n~~sn. Afters a con'Cacz 'CimP of ' FO minutes,' 1 ml of n the tp:;r, microbial suspension is iemuved, ;and the ~~~~
.
number of tnicZ~vbes j t1 'the Lest mi x;t-rF is det~~rmined.
, After eXpiry ~f this time the number of miczc~Les has ii, ' :, reduced from 10' to 10' . ' . ..
' :
I
~xam~ie 4: . ~ .' jr ..
.
~.._ .
b g of _i-~minopropyl vinyl cthor ~ (~rldrich) , G~ g ' tcrt-bui~yl methaoiyldl:e (Aldrich) and 6U ml nfi; ai-hanr~ls~
.
ara rhar~ecl to a three-nackcd fla;~)t ~ ~nnd heated ' to .;.
under a stiecuu of argOri. 0.'15 g nt E a~~hi.s- ' .'.
isobutxrnni fri.le dissolved in 9 ml of. ethyl mothyl ~, ketone :_s then alcwly added dropwise. with s~irrinc~_ The mixture is heated to 70C and etirrcd ~t this tompcrature for 72 ii. ArLei explry! o:C this dime the ~' '~i :
.
reaCtior_ . mixi:ra is stirred into 0.. 5 1 of doionizc~3 ,.
.?0 water, vhereupori the polymdzic Y~c.~auc:L pi-ec:l~itates.
Hfter >:~.lteri ng nff the product, th~ filter laakc io ' r ;
. :
a waohcd with 100 ml of deiuiii::ed w~l.e.c' Lo rembve ari~~
!
i . The product '?.s then monomer residues ~t-i 1 1 present ;
, ;
. ~ ., ~
dried in vacuo Lor 24 huui5 dl 50C.
;
' 2 5 . ' ! '' 1 , Exile .~a: . : , :
0 . 05 g o ~ the prncir.i: from ExamrlQ 4 ! is shaken in , ml : '..
.:
of a i:est microbial ~uspcn~fon of 3taphy~oW'W :qua ' 1e ml of v aureus . Alter 8 ' Contact time c~f 1 5' mi nnt-p5, 3D thQ test: microbial cuopcnoion i3 . remov'ed~ end the ;
numL~si o r mic:.cobes in the tPSI: m1 xi-:nra i s dararmi nen. ' ' After Expiry of this time staphylococcus . aureu;~ ~. .,, ,, microbes dre rw longer detectable. ' '';.
.
s:
. ;, r, . ' ~:
~ 5 Expm~rirt ~I~ : , . : , I .. ~
~
.
..
.
0 _ w75 c~ n.' the product from Examplo 4 'ir ohckcn i~ 20 ml of a tesL microbial suspension of PsPU~clnmnna:~
aeru~inn:;a _ 74.fter z contact time of 6j0 mix~utc~, Z ml of , the teat. microbial au5,~emlon is removed, amcl the . i '' i ' ;
;
i . ii . v h ' ' . a :, . . s .!
.
r ' . ' . . .
'~a 08/x2 a2 U8: 93 FAX ErU9SA MARL, IPM , ~-~-~ GA FETHER,STnN ,I, FR ' ' Id CA 02383030 2002-02-21 , - 16 - ; ~ " .
number of microb~s in the test: mixtut~e is de'~ermine~Y.
'' . After cxpiry of ~xiis time .'"
'Che nmher of mic~obos hus .
V:
reduced tram 10' to 10~. , _ . 'I
;n i j ' 5 . .., Exrc~l~ 5. , ~ . : i, j a ~ n .K
11 nylon 12 filiu is exposed for ~ mi_nutcs at a jpreEOUre j of 1 ~Irit:ar to 172 nm rsdiat~.on from, a Hera~su5; excimor';' .:
Source. The film activated in tri:, ~wa is y plabo.d into ;
. an irradiai-c,r under an, inert gu3 arid seCUred. j U11I,~Gr a ' ~ ' ~
counter:.l.ream of filler L Qas. the fi ~1 m i .s thQn j :..
coverEd with ZU . m I of a mixture of 6 g of 3 aminoprop~,r1 vinyl :~
cthor (,~ldrich) , 6 y of butyl methacry:LatP (~R I Sri eh) and 60 c~ ~t athznol. The irradiatiori chamber i~ sealed.
.
and ple ced at a distance 0I 10 'Cm =rom a a HPlraPL7S ' ' i . 15 excimer srn~rce emitting at wavolongth 308 nm.
Irradiation is Ldc.~un and continues ror :l5 minu~:c~~_ ~~hea 1 rilm ~i~ 1-.han romoved and rinsed with 30 ml of ethamol.
'' The filrrv is then ~l.clea ror 12 hours at 50~ in varnn_ ,' ThP t'i~lm is than ~xtracted in wator fvr 5 time3~6 houxa i~
' 20 at 30C, then dried Lui 12 hours at 50"G. , i '.
::
., ' The rev~trse side of ~ the Lilm i5 l.l~cn treated] in 'Che ;u~
:
same way, so that: tha ny1 on film finally obtaljned has ~k . ' bCCn COated On both Sid~S ~ W1t11 y1_d.~1,4(~ ~Ulylll(ar. ;t .
i I
2 5 ' i ' ~ ~
Example 5s: :<
A piece Of cnatPrl film from Example 5 (5 x 4jcm) is nhakon .i_n 30 ml of a test zmioloLial ,~uapeW 1VU vL ~ ~S~' ' StaphylOi:oCCUS aura~.~R . . After a contact time '~ of 15 s' ~~ .:
30 minutes, 1 ml of the test microbial sus~ron~ium is ..
' zmuuvea old the number Of mi r.r~ha~ i n t-hP t-PCt :mixture is de~ter~nin~d. After cxpiry Of thl3 time 3taphyljococcu:
. our cus ni:Lc:xuk~es are no longer detectable ., i ..
' I~
. . . ..
~J ~'rX~IAp'11~ 7~: ' .' A piece of coated film from Examp~.e 8 (5 x 4 ~ cm) is .
shakers ~:~ 30 ml of a tes~C microh:i ~ I ampen~ion of PReuclnmor~as , aeruginosa. lifter a' COiltaCt tiulB ~ of GCi minutes, 1 a:1 Or the Lest mic:.r~hi ~~ i susren~ion is _:
:
A :
f ~ i 1. ;
ii~
' ' ~ . ~ is ,: . i , 08/42 42 48' 3d FAZ ErLT,SSA MARL, IPA ~a~ C.A FET~RSTON , FR . , I
id . , :;~
' - 7.7 -If removed anrl the numbor o f microbes in l.he tes'~
mixture is detcrmi.taed. After expiry of this rime the ;"
umber o microbe.; has rPducad from 10' to 109. ; . . ' ! ~a :
.r7 , .
EXdittP.l~ 6 I f!
I
, A nylon-12 film is exposed for 2 miriutP9 ~t a jF
jrressure of 1 mk:ar Ln 1'7~ nn radiation frog a IIcraeus~ , cxc:l,iut~r oource. The film activated in this way is played ';
into ~
I
an irra~.iiat-nr under an inert gao and secured. i.
Under d , ;;
countcr::.tream of 111ei 1. c~as, the Iilm i s covered rhPn i with GlJ ml of a mixture of 6 g of 3-aminoprop ~l vinyl ! ether (111drich), 4 y ur rert-butyl meth~crylatr 'f, a) ' (.Aldrict~) and fief 7 of ethanol. fhe irradiation chamber iE esoal cd and plaeca at a, aiSLdcice of 10 Cmf '' from a ~
~
Heraeus exCilner ;' Rni.~r.ce ~mitting at ?wavelength f308 nn. ~N
. ;:
Irrad~.ation is begun died continues for 15 minul~es . The . i;
film is thRn removed and rinsed w:Ltl~ 30 ml of , ethanol.
The filn. is then drips ru.c 12 hours' at 50"G
i 11'~ vacuo. ..
, The tile: is i-hen extracted in water for 5 times . 6 hvura ' 20 at 30C, then dried for 12 lmu~a al, 50C. ! :
'' .i ..
:, ::
The rcvr:r.3e side of the fillu is ~ Lli~aci Lredl.ed i 1n the same wa~i, so thaC the nylon film finally ~obtaijned i:
has is been coated on both sidr~,~ with grafted polymer. :
' .il~
:;.
z~
s I f >ex3mplo ~~,s : i ~.
. . ..:.
.
' E
' A piece of coated film t'rnm Fxampl a , ~ , ( ~
5 x d i cm) is ,;
, i . _ shaYpn 1,n 30 ml ofi a tout, microbial auspen.~'sion of , Staphylo~:occus .aureiis. , A~i Rr , contact time ~
of 15 ,,~
' 30 minutes, 1 ml of the test microbial suspension s:
is f 's zeutuvea .3tid the number cf' mi ~rnhas i n tt,P ;h tP~t ~mi.xtura is det~r~ained. lifter expiry of this t~~.m~ 3taphyl~ococcus .
h ' i ;
aureus m.? ca,wk~es are no longer detectable. ...
j ' .:
v'!
.i :
, .
.
3b nxampls s~l~ ~ ~ : ' :' .
;;;
1~, piece of c:nated film fxom ExamplQ; 6 (5 x :,
:
in rtlrn).man Patent Application 0. 972; 512 and baled o~~
a ~.
graft pc.~lymerizativci or monomer molecules and ihii-.i ai-nr . s.
ma 1 Rr. i P s . incorporated by owe 11 ing . The mononEer used for the ~wallirm may be component .~1. j ~.
' 15 . ' ' Even wi~.hout grafting onto a substrate surtar.A, the novel alntimirrobial copolymers o1' vinyl cthcr~! of the , . ~ general formula (c:muputmnL I) , 'in parLlCl~lar _3-- , amin~prr.pyl vinyl ether with at least. ono aliph~tically y ;
. 20 unt;atur~ted monorcver (cmu~ruueuL~ II) show microbi.~~.dal i or ~ ..
.: ;
antimic:.rohi~l hahaviour_ Another embodiment ~oi' the :
., prcocnt invention w~txsi~ L,~ iii e:ci.i'L'yiny o~.tt the ::
copOlymefiZatlon nt ~nmponentR T andII on a sub~5trate. ~
. 2 :, . ~ ; . I
Z5 The componpnfi~ may be in~ solution when applied to thv ;
subatrat~s. Examples uL sui~aT~lc~ solvents are; water, ~
ethanol. methannl , methyl ethyl ketcine, diethyl; ath~r, ' dioxane, hcxax~c, heptane, benzene, toluene, chl~Lofumu, , diChloro~aethane, te~i-.r~rly~r~for~n and acetonitr~lQ_ Ii:
;
30 i~, also possible to use component 'II as solvent fog: .
; i couyu=len , I . , .
.;, , . ; }~
i :'i The muv~~1 arrLimicxobial copolymers ' may also kip mach e;' . ,1!
.. , ' directly, i.~. not by polymerizing the components on << > t~
suL~t~aLF: bud as an antimicrobial ; coati nQ_ ~~ni tah'.l~r~!~
c~.c,at'in~ m4thods are application of 'the copoly~nera ire ~ iP
SCtlut1011 uZ d5,d melt.
, = i .
j . . : . ', ' ' o:
i . I
. . . . .
' ' "
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i 1.1 ' .. :N
' ' ' i . .
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t l!
o2 FR 48' 31 FAa EGUSSA MARL. IPM ~~- C.A FETaERSTON. , Q8/0 2 , IQ
n19 CA 02383030 2002-02-21 . ~i~
y ~
ji 1 ~ - . . ~, . . , ; . i Thp solution of the novel polymeiw may be ap~liec~ I-n :;
the aul:~atrate5 by dipping, ~sprayin.g or pairsti.ng, for '..
examp'i a . . : ~. _' ;
'' ' :
~ s;
~ ~ :..
, ,..
. 5 , ~r i >= the novel polymers are u~ea~ directly I on the ~
,.
y substraU:e ~5urfaee without: c~rafting,v conv~nt~.on~l free ;
j ~i r~riiral initiators may be added. ;
y, ' t ~ ;
Exampl R::: of initiator , ;
which . may' be us~:~l . iss the !: t .
' ' 10 preparation of LW novel. copol ymara ' arR~, inter alts, a~nni trles, alkyl pcroxide3, hy~lroperoxirla~, dc:yl , t peroxides, pezuxuY.etones. pere3ters~ peroxorarhnnates, ~~
t o :r pProxodisulfate, peraulfatc and ainy of the usual photoinitial.ut'S, such as arPl~ophRnr7na~, a- , ; t 1.5 hyc~rnxy~-etonvs, ,dimethylkctalo t~rsd ~ benzophonone .
The ~' ,k ' polymeL~ cal.lon may also be 1rii'tiate~l. thPrm~1 1ynr, .'.' ~as .
.
a 1 re2d,y stated, by electromzgnctic 'radiation, auC~x a3 .
W light or y-~d.raldLiOn. .
t ~ ~ is 20 The novr:l ruutimic:robial polymers mar also be ;used as , ~nmrnnents~ for formulating inky, p3into o~ other surface coatings. , ' t ;~~
' ; ; .w .
:
..
Use of t:~c modified polymetr auL~L~~al.~s .";
G5 The prp:;sni-. invention also provides the use ~ of the ', 'ui ;, novel anrimicrubidl pulymeiw l.u produce antimic~obially aotiva l~rnc~,.,ots, end the products por so which are v!
. :
.
produced in this way. Tlse pLUauul.5 rosy C;UlIl~1'luC ipUlylll.el'.
~ t;
S11hS1'.ratms modified according to ;the invcntivn on ' 30 pe dLe ,pL~r~rably a '.
conaiot of these. Products of tlui~ ~y , based ors po7.y~mi ~fPS, rolyurathanes; polyether block t amidos, polyc3t~ramidea or -imidea, PVC, poly~7.afim, ~ is s', Sillcone;a, polysiloxanta. polymethacrylatP or; p~ly-t;
t~rQphthrWatoa which are surface--modifiied uaini~ novel ;
., 35 . . ;c pulysuers.. . ' ~ .
. .
. ~ ;:
t :k Exd.xuFsles ~of antimicxobially active ; pr~cinri-~ cif this type axo ix~, particular mnchine parts rod food pltJlaiD~llLf~, components ~.n a 1 r-rnnp tinning systems, .!;
' t .lt ~. ' a , 1 . . t -:
~ . ' I
:
OB/02 02 FR o8 ~ 32 FAg ErUSSA MARL, IPM ~~~ CA FETRSTAN , IQ
pid ., CA 02383030 2002-02-21 . ~;rj o ;:
' ' ~i - 11 - , :.
rooting, items for bathroom and tuilc~L use,! kitchon items, components ur sanitary cquip~n~nt, comp. r~ents of CaCreS cr hOlIRRS for animale, recreational pZUC~ uc:ls for childr~;z, components u.C wdLer systems. rood p~ ckaginc3, Oj7~Id(.U:_' units (roLich pan~ls) of device's, and l conLac:L
~. .
r lenses . ~ ; s :, .
;~
fho novol cvpalymers ur Graft copolymers ~ may I tip LlSQd anywher~:~ where imrortance is placed on Surfaces YVl.th '..
! 10 release pxop~srties or suz,Cdc:eS which, are 'very ffPP tram ', baCteri, i.P_ mi.crobicidal. Fr..amplo~s of opplic~.tion of the nv acl ~ CQpOl~lmGl ~ uL' y.~~att ' polymers fare in ' partieu7 ar ~ snrt'ace coatings, protective pai~2tt~ and v other ec:atinga in the fulluwiiiy 5ec:l.t~r's : ~ , a ' 15 ' ' ' Y
il~
- Marine: Boat hulls, c~u~k5, . buoYS. ctrillinq a pl.2tforms, h~7 7 ast water tanks v rr ..
' - con ,truction: Rvofinq, Laseumu~5, walls. facades.
a greenhomP9, Burr protection, g~rdan fencing, wood 20 protection ' 5anlLary: Pnh1 l c conveniences, ' bathrootns, ~ shower .
' cur trrina, toilet items, swin.uuit~y Yuul, . ~dunar l -~oiztinc_i', sealing compounds ~r .
, ~ tchen, Mz~c:hiriea l - Reqwisitoa foe daily l~,fe:
l 25 kl~ ;hen items. sponge pads, recrear.iona.L pr~dnrt:a ..:
for children, food packaging,; milk pro~aasingr '.
. ' ' ' drl:~kinc~ water systems, cosme_tir.,.s ' ; .
, ion - Machine party: llir-Conditioning systems , l ; ;, exchangers, process w~tPr, ~c~~ i%iT'-~)C7W?1'PC,i . units, r . l .
' 30 hew:. exchangers, bioreactora, membranes : ;~,v I l SJ
= Mea.ic:dl technology: t:nni-.arr :1 pngaa, rii aper, s, . : ;.
memi~raner, implants ' .' .>>
- cun;ju~u~r articles: l~utomobile seats, Clothing 3 (souks,~ sports clothing) , hospi'i~al cquipmcr>!L, door. a !
:
: .:
w 35 hant~Zca, teld~rnu~xe tmc~dbe~s, public conveyances. ,r l anin.Wl caQA~, cash registers, wall;to-wall.
, ' carpets, , wallpal'rr.c s . .
. . .. fl.
. ~
.
, ".a . ' , ' . .;r l .
' . ~ .. ..
t P
:..
. . x ' ' . . . ..
. ..
. ~ ~ . . l:
'.
Os/02 n2 48.32 FAg ErUSSA MARL, IPM . --~~ CA FETHERSTON ~~, FR td~i5 :
.
CA 02383030 2002-02-21 . ':
. . ' : " ~~;
- 1~ - ..
. .; ..
; . . . ~~
.
Z~he rJrPS~.lTtt ihVaritl.Oh al:lO provid~ss~ ' rOr the use of thc~
;:
novel ;?olymcr ~ubstxates, whngA surfaces h~vo bees 'i modi.rie~x ming novel polymers 'vr ~JZUC:e55~fS, ' for ' ' producing hygicu~ products Or . i tams in medical ..:
~
~tchnology. ~nhat which has been said above. uNmeerning preferrsad materials ap~alies Correspondingly_ ~p ~Rxampl~es .
yr tiyq:. ene prodnrt~ of this type: arc toothSbrushc;:, ,.
'toilot ocats, 'combs dmci packaging mateZials. iS
'the term "
hYqiene item alga includes othwr ob~octo which inay conic into contact With a latue mut~~er of. peopl p, gt~rh as ;
' telephor,P handsets, stair. railo, door h~ndlcs; ;;
Willl'~VW ,~
catches, and graL S LL'a[J5 and grab ' handles irk ph1 i c i convayai:ra~_ Exssnples of item.a in :medical f':
tcGhnology a:
arc catheters, tuLiy, ~.)L'ULecLlve or backing '.
films encl. ~
a ;:
also surgical in~tr~.~ments . ' . ' r ;(:
';
' . ~, i:
s.
,, The tolloWirig examples are given in, order to ~.escribo the pror.~cnt inPentian in greatcl ~lel.d.il, r ~ul. ~c~,re not ~ ..
intended to limit its scone as set~out in the , patent 2 0 clai~na .
.
ai ~ , ..
'.
:.a $xat~plc 1: ' ' s' ' ; ~.
' 6 q Of 3-aminopropyl viny I ~ rf'hPr ' (A1 ~iri rh ) , ; E'., g of ~~
methyl aiotho.crylate (Aldzich) and G0; ml of "!' cth~liol aie ' ;, charged Lo a three-neckPr! t I ask ~n~i h~ai-aci ~o ~S"n ~n . under a ctreain of argon. , . 0.15 [g oz" , ':
.
.
acobisis:~butyronitrile dissolved. iri 4 ml oir :
ai~hyl ' n . ~ ~
.
z~nethyl .cetoiie is then alowly added dropwisd, ':
with i ~
:
stirring. The mixture is t'lP~3fiPf~ 1-W '7;17(".
~h~i ~ati~.r.rer_l at ,:
this temperature fox 72 h. After cxpiry of this ~"~
time : ' the r~ae; ~ium tulxture is stirrP~I i nfin ~ iJ
. ~i I nt rl~si onized ' T
water, whcreu vn the .' ':' p polymeric pro~3uct precipitates.
I !4 Rfter tille.c~.inq oft the product, Lhc filter ~:akp i washed orith 100 ml of dc~.or~i~cd wu~Ler to rembvc '"
an~r 'y ' 35 monomer resirlud5 5L111 present. The product ~.s them ~i dried i,u vacuo fir ~a hours at 50C.
.
t ,:
' v yh ' ~ :1.
, .
.
i . ' i . y .
. . I
~
i 1 . . . :h :i)' i . ; i d":
I ,i"
' ' i ' 48./42 48' 92 FAY EGUSSA MARL, IPM ~~~ fA FETHERSTON, ; Id , ., CA 02383030 2002-02-21 I'' ' . . a~:
_ 13 . . . : <:
, ~ ..
E~a i .
0 . O5 g ~f ~xie product trim Example I is Ehakcn in 20 zal ~f a tort micrvbicl suspec~slon , or 5taph~.l nrr,rcvs aureus. ALLer a contact- time of 15 mi'nute~, '..:
i1 ml of "
rrte tra.=:t microbial auapensium 15. removed, , land i:ha ~' , number of microbes iri the 1-.Rqt- mixature is de~eizaincc(.
iF
After Pxpiry of this time Ota~hylowuuus~ aureus ', ' microbes al'e 11U lonqer detectable. . . . ;):
~
,.
.
.
EXample 1b: , i , . ' U.()h r~ r.:~f the product from Example 1is shaken dim 20 ml ' i :
; ~
of a ta5l. microbial suspengi ~Ih of Pswhdomonas ya ' :
aerugincsa. After a contact time of ~i0 zuiiiul.e5, ~
' Z m1 of -tlw les ~ microbial suspPnsi nn i ~ ~ rPmwed, '.r end th~ ~~ :
:
, number c,f microbes in the teat mixture is det~rminea. :
a vi ,.
' After e~:pi.r:y of this' time ~Che numhPr nfi mi nrrjhes has rs~dtma~l from 10' to 10c . ' I
Exat~rls 2:
I . . it 6 g of 3-aminopiu,~yl vinyl ether. '(Aldrich). 6 g of .
hntyl mr:~thacrylat~ (Aldrich) and 60; ml of cthr~nol are iY
charged to a three-necked flask arid heated ~0 65t.:
under n stream of a~'yon. ~ 0. ~.5 ;g o:~
.
~s~obiaia~butyromiL~ile dissolved 11~ 4 ml o~ ;
ethyl ~ .
:
. ;
~5 methyl cpt~na is them slowly added dropwise, with _ !
'. a stirring. The mixtu.ce i5 tieaLed Lo 7:0"C and st~fred a1:
this tenpArarttra far 72 h_ After expiry of this time , the reaction mixturo is atirra~l iiitu X0.0 1 UL t~Erj.u111GCC~
water, mherPUprtn the polymeric prosiuct precipitates . , l~ftor f; ltering off the product, tIm filtez 'y (:eke i5 washed with 100 mi of cieionized water to r~mpv~ ' , any n4 monomer rc~idue9 still preseazt. This ~rLUCiu4~
is l.hen dried iz~ vacuo for d9 hnur~ ~t ~7Of._ : ' ;j;
:
., .: c s, ~
r ~ i 3u Ex~uupl~ .?a: . : a~.
1.
~ . 0.5 g o. th~ product from Exazuple 2, as shaken ~_:
i~a 20 m7. ~
of d l.e5l. microbial Suspension ~~f ~t-arhyLococcus j ~lSrpW . After a contact . time of 15 v minutes, ~w 1 ml of the test: mioiuLial Suspension is .:'removed, ~nh the r n 1' ~f I i h 't ' . i.
j i I
I . . 9 , j ~ ' , a . ~ ~;
08/02 02 08 93 FAY ErUSSA MARL, IPM -~~ CA FETHERSTON .~
FR I~
01~
CA 02383030 2002-02-21 :
' - 14 - ~ . . ;:
nLUribpr nfi microbes i.n tho test mixture i8 deLermin~cj, :
( I
lifter expiry of this time Staghylococeus; aureus , ' ';.
microbe. ara no longor detect~xble. . . :.
S Ex~Dle 2h i 0.05 ~ f the ~' ~ ' '' J p'rwduCt from l;xa~p.l p ? is shaken ;in ~0 ml ~
; ;;, I oI a 'test microbial cuvpcnsion of Pae~ut.~omonas acruginc~sa. Aft~aw a contact time of 'HO minutRS,' ..f X ml of :
the te~:L mirrc:,bial suspension i3 , removed, hand Lh.e 10. number r.~f microbes iu , the test m~xturP i a a;
. clPt~rmined. ~
~
v After eapiry of this ti.m9 the number of mi4rqbes has '..
1 ,.
; .. .
. reduced from 10' tc~ 20' . .
. , .i .
=i ' Ex~pl~ 3: ' , ~ ' i 15 . ..
6 g ~f :3-aminoproPyl vinyl ether (Aldrich) , G ~g of 2- ~
?c diethylamimuel.lAyl methacrylate (Ald~ich) anti ?'.
fl7 m1 of '' t.
.
. ;
ethano I are charged to s three-necked flaals and hee~t~3 ' to 65r: under a Stream of argon. 0.15; c~ ~r ~~ '"
a azobisisobutyrc,r,i trile dissolv~d iri 4 ml of ;r ethyl ~;
20 methyl ketone is then slowly aac~ea cWopwlse, with . stirring . '1'hR mi xtura is heated to 70C and =r . st~!rred at ;' ..:
f .
thi.o temperature fp3; 72 1~. ArLew eispiry of this time the reaction mixi,ur,e is stirr~d intvØ5 1 of d~ionized water, whereupon the pvly>.ueilu ~rvld.uct t~reci~itates.
.~
25 After tl.ltP.ri nc~ off tha product, the filtor fake washed ~,~ith 100 ml u.C deionized water to remove aii any ' ztloriomer resich~as still present _ The product is then _..
:;
r I
.. H
dried in vaCUO for 24 haura at ~0C. ' i ..
a :
' l::
, ' 30 Exa~mplc 3a: : " ~~I~
.. ' ;.;
0. OS 5~ v C the Droduca from h;xamp i P B .; ;;
s shaken ',in 20 m~. ;
of a test microbial suspen'ion ~of utaphyloco~:cuu j auteus. RrLer a Contact time of 15 mi.rn~tP:~, ~ m1 of i the t~sT: microbi.ul suapenaion is : removed, a~n ~l :~llr.
a 35 mulula~L~ u.t microbes iri the t:PSt mi xt~~rR y i ~ rlPt-~.'~rmined. ' pftar ex(~iry of this time the number of microbes ~~~
has , reduced frc:uu IO' to 10' . , n . . I
..
I :' II
.
' ~ 'A
. . ~ ~I
r i , n . .1 I
. :s ~ ~ .. .
08./p2 08' 33 FAZ EGLtSSA MARL, IPM i~~ CA FETBERSTON i~
,.
CA 02383030 2002-02-21 ' . - 15 - , ' ~ ':
Example jb: : ' ' .
:
0. 05 g of.: the pzuc~uct from bxamp I a .3 is shaken din 20 ml a , :;
of a tact microbial suspension ur Ps~udomohaS
aorug~.n~~sn. Afters a con'Cacz 'CimP of ' FO minutes,' 1 ml of n the tp:;r, microbial suspension is iemuved, ;and the ~~~~
.
number of tnicZ~vbes j t1 'the Lest mi x;t-rF is det~~rmined.
, After eXpiry ~f this time the number of miczc~Les has ii, ' :, reduced from 10' to 10' . ' . ..
' :
I
~xam~ie 4: . ~ .' jr ..
.
~.._ .
b g of _i-~minopropyl vinyl cthor ~ (~rldrich) , G~ g ' tcrt-bui~yl methaoiyldl:e (Aldrich) and 6U ml nfi; ai-hanr~ls~
.
ara rhar~ecl to a three-nackcd fla;~)t ~ ~nnd heated ' to .;.
under a stiecuu of argOri. 0.'15 g nt E a~~hi.s- ' .'.
isobutxrnni fri.le dissolved in 9 ml of. ethyl mothyl ~, ketone :_s then alcwly added dropwise. with s~irrinc~_ The mixture is heated to 70C and etirrcd ~t this tompcrature for 72 ii. ArLei explry! o:C this dime the ~' '~i :
.
reaCtior_ . mixi:ra is stirred into 0.. 5 1 of doionizc~3 ,.
.?0 water, vhereupori the polymdzic Y~c.~auc:L pi-ec:l~itates.
Hfter >:~.lteri ng nff the product, th~ filter laakc io ' r ;
. :
a waohcd with 100 ml of deiuiii::ed w~l.e.c' Lo rembve ari~~
!
i . The product '?.s then monomer residues ~t-i 1 1 present ;
, ;
. ~ ., ~
dried in vacuo Lor 24 huui5 dl 50C.
;
' 2 5 . ' ! '' 1 , Exile .~a: . : , :
0 . 05 g o ~ the prncir.i: from ExamrlQ 4 ! is shaken in , ml : '..
.:
of a i:est microbial ~uspcn~fon of 3taphy~oW'W :qua ' 1e ml of v aureus . Alter 8 ' Contact time c~f 1 5' mi nnt-p5, 3D thQ test: microbial cuopcnoion i3 . remov'ed~ end the ;
numL~si o r mic:.cobes in the tPSI: m1 xi-:nra i s dararmi nen. ' ' After Expiry of this time staphylococcus . aureu;~ ~. .,, ,, microbes dre rw longer detectable. ' '';.
.
s:
. ;, r, . ' ~:
~ 5 Expm~rirt ~I~ : , . : , I .. ~
~
.
..
.
0 _ w75 c~ n.' the product from Examplo 4 'ir ohckcn i~ 20 ml of a tesL microbial suspension of PsPU~clnmnna:~
aeru~inn:;a _ 74.fter z contact time of 6j0 mix~utc~, Z ml of , the teat. microbial au5,~emlon is removed, amcl the . i '' i ' ;
;
i . ii . v h ' ' . a :, . . s .!
.
r ' . ' . . .
'~a 08/x2 a2 U8: 93 FAX ErU9SA MARL, IPM , ~-~-~ GA FETHER,STnN ,I, FR ' ' Id CA 02383030 2002-02-21 , - 16 - ; ~ " .
number of microb~s in the test: mixtut~e is de'~ermine~Y.
'' . After cxpiry of ~xiis time .'"
'Che nmher of mic~obos hus .
V:
reduced tram 10' to 10~. , _ . 'I
;n i j ' 5 . .., Exrc~l~ 5. , ~ . : i, j a ~ n .K
11 nylon 12 filiu is exposed for ~ mi_nutcs at a jpreEOUre j of 1 ~Irit:ar to 172 nm rsdiat~.on from, a Hera~su5; excimor';' .:
Source. The film activated in tri:, ~wa is y plabo.d into ;
. an irradiai-c,r under an, inert gu3 arid seCUred. j U11I,~Gr a ' ~ ' ~
counter:.l.ream of filler L Qas. the fi ~1 m i .s thQn j :..
coverEd with ZU . m I of a mixture of 6 g of 3 aminoprop~,r1 vinyl :~
cthor (,~ldrich) , 6 y of butyl methacry:LatP (~R I Sri eh) and 60 c~ ~t athznol. The irradiatiori chamber i~ sealed.
.
and ple ced at a distance 0I 10 'Cm =rom a a HPlraPL7S ' ' i . 15 excimer srn~rce emitting at wavolongth 308 nm.
Irradiation is Ldc.~un and continues ror :l5 minu~:c~~_ ~~hea 1 rilm ~i~ 1-.han romoved and rinsed with 30 ml of ethamol.
'' The filrrv is then ~l.clea ror 12 hours at 50~ in varnn_ ,' ThP t'i~lm is than ~xtracted in wator fvr 5 time3~6 houxa i~
' 20 at 30C, then dried Lui 12 hours at 50"G. , i '.
::
., ' The rev~trse side of ~ the Lilm i5 l.l~cn treated] in 'Che ;u~
:
same way, so that: tha ny1 on film finally obtaljned has ~k . ' bCCn COated On both Sid~S ~ W1t11 y1_d.~1,4(~ ~Ulylll(ar. ;t .
i I
2 5 ' i ' ~ ~
Example 5s: :<
A piece Of cnatPrl film from Example 5 (5 x 4jcm) is nhakon .i_n 30 ml of a test zmioloLial ,~uapeW 1VU vL ~ ~S~' ' StaphylOi:oCCUS aura~.~R . . After a contact time '~ of 15 s' ~~ .:
30 minutes, 1 ml of the test microbial sus~ron~ium is ..
' zmuuvea old the number Of mi r.r~ha~ i n t-hP t-PCt :mixture is de~ter~nin~d. After cxpiry Of thl3 time 3taphyljococcu:
. our cus ni:Lc:xuk~es are no longer detectable ., i ..
' I~
. . . ..
~J ~'rX~IAp'11~ 7~: ' .' A piece of coated film from Examp~.e 8 (5 x 4 ~ cm) is .
shakers ~:~ 30 ml of a tes~C microh:i ~ I ampen~ion of PReuclnmor~as , aeruginosa. lifter a' COiltaCt tiulB ~ of GCi minutes, 1 a:1 Or the Lest mic:.r~hi ~~ i susren~ion is _:
:
A :
f ~ i 1. ;
ii~
' ' ~ . ~ is ,: . i , 08/42 42 48' 3d FAZ ErLT,SSA MARL, IPA ~a~ C.A FET~RSTON , FR . , I
id . , :;~
' - 7.7 -If removed anrl the numbor o f microbes in l.he tes'~
mixture is detcrmi.taed. After expiry of this rime the ;"
umber o microbe.; has rPducad from 10' to 109. ; . . ' ! ~a :
.r7 , .
EXdittP.l~ 6 I f!
I
, A nylon-12 film is exposed for 2 miriutP9 ~t a jF
jrressure of 1 mk:ar Ln 1'7~ nn radiation frog a IIcraeus~ , cxc:l,iut~r oource. The film activated in this way is played ';
into ~
I
an irra~.iiat-nr under an inert gao and secured. i.
Under d , ;;
countcr::.tream of 111ei 1. c~as, the Iilm i s covered rhPn i with GlJ ml of a mixture of 6 g of 3-aminoprop ~l vinyl ! ether (111drich), 4 y ur rert-butyl meth~crylatr 'f, a) ' (.Aldrict~) and fief 7 of ethanol. fhe irradiation chamber iE esoal cd and plaeca at a, aiSLdcice of 10 Cmf '' from a ~
~
Heraeus exCilner ;' Rni.~r.ce ~mitting at ?wavelength f308 nn. ~N
. ;:
Irrad~.ation is begun died continues for 15 minul~es . The . i;
film is thRn removed and rinsed w:Ltl~ 30 ml of , ethanol.
The filn. is then drips ru.c 12 hours' at 50"G
i 11'~ vacuo. ..
, The tile: is i-hen extracted in water for 5 times . 6 hvura ' 20 at 30C, then dried for 12 lmu~a al, 50C. ! :
'' .i ..
:, ::
The rcvr:r.3e side of the fillu is ~ Lli~aci Lredl.ed i 1n the same wa~i, so thaC the nylon film finally ~obtaijned i:
has is been coated on both sidr~,~ with grafted polymer. :
' .il~
:;.
z~
s I f >ex3mplo ~~,s : i ~.
. . ..:.
.
' E
' A piece of coated film t'rnm Fxampl a , ~ , ( ~
5 x d i cm) is ,;
, i . _ shaYpn 1,n 30 ml ofi a tout, microbial auspen.~'sion of , Staphylo~:occus .aureiis. , A~i Rr , contact time ~
of 15 ,,~
' 30 minutes, 1 ml of the test microbial suspension s:
is f 's zeutuvea .3tid the number cf' mi ~rnhas i n tt,P ;h tP~t ~mi.xtura is det~r~ained. lifter expiry of this t~~.m~ 3taphyl~ococcus .
h ' i ;
aureus m.? ca,wk~es are no longer detectable. ...
j ' .:
v'!
.i :
, .
.
3b nxampls s~l~ ~ ~ : ' :' .
;;;
1~, piece of c:nated film fxom ExamplQ; 6 (5 x :,
4 ~ caa) io 3 . : .
shaken ~n 30 m~ of atest microb~.al suspension rif :p YsstWcmr~rms aQruginosa. After a contact time ~ .of GG
''. minutes, 1 ml u1 l.lre Lest m~.croblal , sugpPn~i ' nn is '~
' . t . :
,~
08.X02 FR 08' 9d FAZ EGUSSA MARL, IPM a~~ GA FETRERSTONII:I
02 ~~J
CA 02383030 2002-02-21 . , ! ~' :i ..
. ~ , ;t ' removed arid the number of microbes .in thd LeSI mixtux'e v i,s dstFrmxned. A~tex expiry of this' tjma the r~umk~ar of ' uucrobe., has rAc~mcQd from ZO~~ to 104:
i ;: '::
:
" . _ . . : ' . . . ;
;h .
. ' i :
I :
.. ,i 1, .
~ :
F:
'.
i il ~
. . ~~
ti ,r ' ' ' ' ,r . f 'fn . a f !I
~
:
.ni f , i 1.
..t i ' ';
i i I~
"
!
, i ' ~
r !
' ?:
! . : ~
>!
. !
. a .
..
' I :;
i ' :.
1 V 1l I ' . V
i , I .' . . ..1 :I
i 35 '. ' ' ?;!
, , ~"r . . i . ~
. . .
j ~ ' ' t i :. :s n ~i I . i ;:J
. . :
i . . ' Y'i ' .
; c ' ,, ! . o ,..
! ..i ' ' i .
i . . , FYI
, ~ i ~ ~
' ' ; , ~ ' e , ' :
, 'yi ' ~
I
'~ ~' n
shaken ~n 30 m~ of atest microb~.al suspension rif :p YsstWcmr~rms aQruginosa. After a contact time ~ .of GG
''. minutes, 1 ml u1 l.lre Lest m~.croblal , sugpPn~i ' nn is '~
' . t . :
,~
08.X02 FR 08' 9d FAZ EGUSSA MARL, IPM a~~ GA FETRERSTONII:I
02 ~~J
CA 02383030 2002-02-21 . , ! ~' :i ..
. ~ , ;t ' removed arid the number of microbes .in thd LeSI mixtux'e v i,s dstFrmxned. A~tex expiry of this' tjma the r~umk~ar of ' uucrobe., has rAc~mcQd from ZO~~ to 104:
i ;: '::
:
" . _ . . : ' . . . ;
;h .
. ' i :
I :
.. ,i 1, .
~ :
F:
'.
i il ~
. . ~~
ti ,r ' ' ' ' ,r . f 'fn . a f !I
~
:
.ni f , i 1.
..t i ' ';
i i I~
"
!
, i ' ~
r !
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! . : ~
>!
. !
. a .
..
' I :;
i ' :.
1 V 1l I ' . V
i , I .' . . ..1 :I
i 35 '. ' ' ?;!
, , ~"r . . i . ~
. . .
j ~ ' ' t i :. :s n ~i I . i ;:J
. . :
i . . ' Y'i ' .
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Claims (22)
1. An antimicrobial copolymer, obtainable by copolymerizing a vinyl ether of the general formula~
where ~R1 is a branched or unbranched hydrocarbon radical having from 1 to 5 carbon atoms, and R2 is H, and R3 is H or branched or unbranched hydrocarbon radical having from 1 to 5 carbon atoms carbon atoms, with at least one aliphatically unsaturated monomer.
where ~R1 is a branched or unbranched hydrocarbon radical having from 1 to 5 carbon atoms, and R2 is H, and R3 is H or branched or unbranched hydrocarbon radical having from 1 to 5 carbon atoms carbon atoms, with at least one aliphatically unsaturated monomer.
2. An antimicrobial polymer as claimed in claim 1, wherein the vinyl ether used comprises 3-aminopropyl vinyl ether.
3. An antimicrobial polymer as claimed in claim 1 or 2, wherein the aliphatically unsaturated monomers are methacrylic acid compounds.
4. An antimicrobial polymer as claimed in claim 1 or 2, wherein the aliphatically unsaturated monomers are acrylic acid compounds.
5. An antimicrobial polymer as claimed in claim 1 or 2, wherein the aliphatically unsaturated monomers used are methyl methacrylate, ethyl methacrylate, butyl methylacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, tert-butyaminoethyl esters, 2-diethylaminoethyl methacrylate, 2-diethyl-aminoethyl vinyl ether, N-3-dimethylamino propylmethacrylamide, 3-metacryloylaminopropyl-trimethylammonium chloride, 2-methacryloyoxyethyltrimethylammonium chloride or 2-methacryloyloxyethyltrimethylammonium methosulfate.
6. An antimicrobial polymer as claimed in any one of claims 1 to 5, wherein the copolymerization is carried out on a substrate.
7. An antimicrobial coating of a substrate, wherein vinyl ethers of the general formula where R1 is a branched or unbranched hydrocarbon radical having from 1 to 5 carbon atoms, and R2 and R3 are II or a branched or unbranched hydrocarbon radical having from 1 to 5 carbon atoms, where R2 and R3 may be identical or different, are copolymerized in graft polymerization of a substrate.
8. An anitmicrobial coating as claimed in claim 7, wherein the substrate is activated prior to the graft polymerization by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge or .gamma.-radiation,
9. An antimicrobial coating as claimed in claim 7, wherein the substrate is activated, prior to the graft polymerization, by UV radiation with a photoinitiator.
10. A process for preparing antimicrobial copolymers, which comprises copolymerizing a vinyl ether of the general formula where R1 is a branched or unbranched hydrocarbon radical having from 1 to 5 carbon atoms, R2 is II, and R3 is H or a branched or unbranched hydrocarbon radical having from 1 to 5 carbon atoms, with at least one aliphatically unsaturated monomer.
11. The process as claimed in claim 10, wherein the vinyl ether used comprises 3-aminopropyl vinyl ether.
12. The process as claimed in claim 10 or 11, wherein the aliphatically unsaturated monomers are methacrylic acid compounds.
13. The process as claimed in claim 10 or 11, wherein the aliphatically unsaturated monomers are acrylic acid compounds.
14. The process as claimed in claim 10 or 11, wherein the aliphatically unsaturated monomers used are methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, tert-butylaminoethyl esters, 2-diethylaminoethyl methacrylate, 2-diethylamino-ethyl vinyl ether, N-3-dimethylaminopropyl-methacrylamide, 3-methacryloylaminopropyltri-methylammonium chloride, 2-methacryloyloxyethyltrimethylammonium chloride or 2-methacryloyloxyethyltrimethylammonium methosulfate.
15. The process as claimed in any one of claims 10 to 14, wherein the copolymerization is carried out on a substrate.
16. A process for preparing an antimicrobial coating of a substrate, which comprises copolymerizing vinyl ethers of the general formula where ~R1 is a branched or unbranched hydrocarbon radical having from 1 to 5 carbon atoms, and R2 and R3 are II or a branches or unbranched hydrocarbon radical having from 1 to 5 carbon atoms, where R2 and R3 may be identical or different, in graft polymerization of a substrate.
7. The process as claimed in claim 16, wherein the substrate is activated prior to the graft polymerization by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge or .gamma.-radiation.
18. The process as claimed in claim 16, wherein the substrate is activated prior to the graft polymerization by UV radiation with a photoinitiator.
19. The use of the antimicrobial polymers as claimed in any of claims 1 to 9 for producing products with an antimicrobial coating of the polymer.
20. The use of the antimicrobial polymers as claimed in any one of claims 1 to 9 for producing medical items with an antimicrobial coating of the polymer.
21. The use of the antimicrobial polymers as claimed in any one of claims 1 to 9 for producing hygiene items with an antimicrobial coating of the polymer.
22. The use of the antimicrobial polymers as claimed in any one of claims 1 to 4 in surface coatings, protective paints or other coatings.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19940023A DE19940023A1 (en) | 1999-08-24 | 1999-08-24 | Copolymers of aminopropyl vinyl ether |
| DE19940023.7 | 1999-08-24 | ||
| PCT/EP2000/006506 WO2001014435A1 (en) | 1999-08-24 | 2000-07-08 | Copolymers of aminopropyl vinyl ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2383030A1 true CA2383030A1 (en) | 2001-03-01 |
Family
ID=7919375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002383030A Abandoned CA2383030A1 (en) | 1999-08-24 | 2000-07-08 | Copolymers of aminopropyl vinyl ether |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1214366A1 (en) |
| JP (1) | JP2003507542A (en) |
| CN (1) | CN1382164A (en) |
| AU (1) | AU6562500A (en) |
| CA (1) | CA2383030A1 (en) |
| DE (1) | DE19940023A1 (en) |
| NO (1) | NO20020767L (en) |
| WO (1) | WO2001014435A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7645419B2 (en) | 2002-10-07 | 2010-01-12 | Basf Se | Killing microorganisms |
| CN102325446A (en) * | 2008-12-29 | 2012-01-18 | 3M创新有限公司 | Antimicrobial copolymer for coating surfaces, obtained by derivatization of a vinylamine-vinylalcohol copolymer |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MXPA02011983A (en) * | 2000-06-09 | 2003-05-27 | Avecia Ltd | Thickeners. |
| DE10110885A1 (en) * | 2001-03-07 | 2002-09-12 | Creavis Tech & Innovation Gmbh | Mocrobicidal separation systems |
| DE10117106A1 (en) * | 2001-04-06 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Antimicrobial food preservation systems |
| DE10150741A1 (en) * | 2001-10-13 | 2003-04-24 | Creavis Tech & Innovation Gmbh | Through-flow apparatus for sterilizing liquid, e.g. drinking water, sewage, process water or liquid or pasty food, is filled with packing bodies or inserts containing antimicrobial polymer |
| DE10205923A1 (en) * | 2002-02-12 | 2003-08-21 | Creavis Tech & Innovation Gmbh | Washing and cleaning formulations with antimicrobial polymers |
| DE10211562B4 (en) * | 2002-03-15 | 2006-09-28 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Antimicrobially modified substrate, process for its preparation and its use |
| CN106310372B (en) * | 2015-06-23 | 2020-05-22 | 上海交通大学 | Degradable magnesium-based intrabony implant drug-loaded polymer/calcium-phosphorus composite coating and preparation |
| CN116323719A (en) * | 2021-08-30 | 2023-06-23 | 株式会社Lg化学 | Antibacterial polymer and antibacterial polymer film comprising same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2980634A (en) * | 1954-10-08 | 1961-04-18 | Rohm & Haas | Quaternary ammonium compounds of polymers of aminoalkyl vinyl ethers |
| DE19709076A1 (en) * | 1997-03-06 | 1998-09-10 | Huels Chemische Werke Ag | Process for the production of antimicrobial plastics |
-
1999
- 1999-08-24 DE DE19940023A patent/DE19940023A1/en not_active Withdrawn
-
2000
- 2000-07-08 AU AU65625/00A patent/AU6562500A/en not_active Abandoned
- 2000-07-08 EP EP00953028A patent/EP1214366A1/en not_active Withdrawn
- 2000-07-08 WO PCT/EP2000/006506 patent/WO2001014435A1/en not_active Application Discontinuation
- 2000-07-08 CN CN00814780A patent/CN1382164A/en active Pending
- 2000-07-08 JP JP2001518763A patent/JP2003507542A/en active Pending
- 2000-07-08 CA CA002383030A patent/CA2383030A1/en not_active Abandoned
-
2002
- 2002-02-15 NO NO20020767A patent/NO20020767L/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7645419B2 (en) | 2002-10-07 | 2010-01-12 | Basf Se | Killing microorganisms |
| CN102325446A (en) * | 2008-12-29 | 2012-01-18 | 3M创新有限公司 | Antimicrobial copolymer for coating surfaces, obtained by derivatization of a vinylamine-vinylalcohol copolymer |
| CN102325446B (en) * | 2008-12-29 | 2014-07-09 | 3M创新有限公司 | Antimicrobial copolymer for coating surfaces, obtained by derivatization of a vinylamine-vinylalcohol copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6562500A (en) | 2001-03-19 |
| EP1214366A1 (en) | 2002-06-19 |
| WO2001014435A1 (en) | 2001-03-01 |
| DE19940023A1 (en) | 2001-03-01 |
| NO20020767L (en) | 2002-04-24 |
| NO20020767D0 (en) | 2002-02-15 |
| JP2003507542A (en) | 2003-02-25 |
| CN1382164A (en) | 2002-11-27 |
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