CA2195744A1 - Hydrophilic coating material for intracorporeal use - Google Patents
Hydrophilic coating material for intracorporeal useInfo
- Publication number
- CA2195744A1 CA2195744A1 CA 2195744 CA2195744A CA2195744A1 CA 2195744 A1 CA2195744 A1 CA 2195744A1 CA 2195744 CA2195744 CA 2195744 CA 2195744 A CA2195744 A CA 2195744A CA 2195744 A1 CA2195744 A1 CA 2195744A1
- Authority
- CA
- Canada
- Prior art keywords
- hydrophilic
- coating
- plasticizer
- monomer
- hydrogen
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
- A61L29/085—Macromolecular materials
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- Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Materials For Medical Uses (AREA)
Abstract
A flexible hydrophilic coating on a device which is to contact body fluid and particularly for flexible substrates on intracorporeal devices such as balloons on dilatation catheters. The coating includes at least 30 % of a copolymer of a hydrophilic monomer and a plasticizer monomer. A presently preferred hydrophilic monomer is acrylamide and the presently preferred plasticizer monomer is methoxy (polyethylene glycol) mono methacrylate where the polyethylene glycol moiety has a molecular weight of about 1000. Other hydrophilic polymers, such as n-vinyl pyrrolidone, may also be incorporated into the coating. Both polymers are treated to attach latent photoactive groups to facilitate the bonding thereof to a substrate.
Description
WO g610316~1 2 ~ 9 5 7 4 4 ~ c j26~
.
HYDROPHILIC COATING MATERIAL
FOR INTRACORrCiRtAL USE
BACKGROUND OF THE INVENTION
This invention generally relates to intraluminal catheters, such as guiding catheters and balloon dilatation catheters used in percutaneous transluminal coronary ally;Oplac~ly IPTCA).
In typical PTCA procedures, a guiding catheter having a p~ ha~Jed distal tip is percutaneously introduced by a Seldinger technique into the cardiovascular system of a patient and advanced within the system until the pl~ llalJcd distal tip of the guiding catheter is disposed ~ within the ascen " lg aorta adjacent the ostium of the desired coronary artery. The guiding catheter is twisted or torqued from its proximal end, which extends outside the patient, to turn the distal tip of the guiding catheter so that it can be guided into the desired coronary ostium. A
balloon dilatation catheter are introduced into and advanced through the guiding catheter to the distal tip thereof out of the distal tip of~ the guiding WO~6~03164 ' 2~1 9 5 7 ~ 4 r~ 3267 catheter until the balioon on the distal extremity of the dilatation catheter--is properly poviliuned across the lesion. Once properly poD;Iiuncd, the balloon is inflated to a p,~,d~ .llli"ed size with r~ .paq~e liquid at relatively high pressures (e.g., generally ~12 aLlllu.pll_,~s) to dilate the stenotic region of the diseased artery. One or more inflations may be necessary to effectively dilate the stenosis. Additional stenoses may be dilatated with the same catheter. When the dilala~iùns are col"ul~ltsd, the balloon is deflated so that the dilatation catheter can be removed from the dilated stenosis and normal blood fiow will resume through the dilated 1 0 artery.
There are several well known types of balloon dilatation catheters which are suitable for coronary a"v, ' :y. They include conventional over-the-wire catheters, fixed-wire catheters, rapid exchange type catheters and perfusion type catheters.
Lubricous coatings have been applied to the surfaces of guiding catheters, dilatation catheters and other intraluminal catheters in order to reduce the coerri,,;_." of friction of the surfaces of these catheters and to facilitate the adva"ccl."~ and v.;ll,d,~.a: of these catheters through various body lumens. For example, silicone coatings have been applied to the exterior of various catheters in order to reduce the coerri~ .,l of friction of the catheter surface, but these coatings are frequently not very durable and lose substantial portions of their lubricity during an intraluminal or intravascular procedure. Durable, lubricous silicone coatings are described in cope.,d;.,g r, 1''-~ Serial No.
WO g6/0316~ 2 1 9 ~ 7 4 4 PcrlussSIOg267 ~ 071913,775, filsd July 13, 1992, but the 8,), '- .- of these lubricous coatings and linings described in the copen ' Iy . r ~ ~ are for the most part co", ' ' manufacturing procedures.
What has been needed and h.,.~Luru~e IJ"~.. ' ' ' is a durable coating for plastic surfaces having long lasting lubricity which does not require cGr", ' ' manufacturing procedures. The present invention satisfies this and other needs.
SUMMARY OF THE INVENTIQN
This invention is directed to an improved i"l".cor~.o,eal device, such as a cathetsr, having a durable, flexible coating which is formed of hyd,ù~Jl 'i~ material and which provides a low COérriuiélll of friction when in contact with an aqueous based liquid.
The durable, flexible coating of the invention is generally formed at least in part from a cOpol,/."e, product co"",,i,i"g a hydrophilic ",onc.",è,ic material and a pl~Li~;iLillg ~"onor"e,i~; material. The copolymer product cu",~u,iaas at least about 50% of the h~/dlopl ' -monomer and from about 2~h to about 50Yo, IJIere,clLly about 5~h to about 30~h, of the plt.;.Li~.i.;,lg monomer. As used herein, all l~f~,.enc to percent refer to percent by weight unless otherwise noted. The co-polymer is treated to attach latent photoactive groups to facilitate the bonding of the reacted copolymer to the desired substrate, as taught in U.S. Patent 5,002,582, which is illcol,uolt~Led herein by reference.
Additional disclosures are found in U.S. Patent 4,722,906, U.S. Patent 4,973,493 and U.S. Patent 4,979,959 which are i,,cor~,u,aLed herein by wo 9CI03164 2 1 9 5 7 4 4 1~ S ~.'C Lti7 reference. The coating formed is a durable, flexible h,/J-opl~ " coating.
At least about 30%r p,ef~,.di,ly at least about 40%, of the coatins should comprise the copolymer of the htd~uul. ' monomer and the plaali~ g monomer. Other i-,y.l,u~Jl ' polymers may be illcul,uOIal~d into the coating to modify coating ,u.ope.li__. The additional hydrophilic polymers should likewise be treated to attach latent,ul,otua~Lie groups as previously described.
The hydrophilic ~u~vlll~ , material forming the copolymer and the hyl.upl ' I"ol,or,l.,lic material forming any hydrophilic polymer illcol~,olc,L~;.l into the coating with the copol~"._. are pltiFe.dbl; seiected from one or more h,~d,upi, ' ",uno,.w,:, having the general formula R,CH = CR2R3 where R, is a hydrogen or pyrrolidone, R2 is a hydrogen or a methyl group, R3 is a hydrogen or -COR", and R~ is -NH2r -OH, -NHC(CH3)2CH2COF,5, -NICH3)2, -OlCH2)nOH, or-OCH3CHCH20H, where Rs is CH3 or OH, and nis1 or2 Particularly suitable ~/dlu,ul ' ulOI-OIIl~la include acrylamide and N-vinyl pyrrolidone.
The ,ulaaLi~ l may be a l~/lluph' plaaLiuia;llg monomer and particularly a pla~ i,lg monomer having the general formula CH2 = CR6-coolcH2cH2o)ncH2cH2oRs WO 96/03164 1 ~ IIIJ,.,~.. ~J~67 ~ where R6 is a hydrogen or methyl group and n is an integer from about 1 to about 25.
A suitable l-.yd,u,ul, " ple.~liLi~;ll9 monomer may at least in part be selected from the group con;.;~li"g of Imethoxy)polylethylene 5 glycol) ",ono",~ll,a- ,ylate, poly(ethylene glycol) Illonolllcllla~ l..t~, Imethoxy)poly(ethylene glycol) acrylate, polyjethylene glycol) acrylate, having a molecular weight from about 500 to about 1500, and mixtures thereof.
The pla~ material may also be at least in part a ~0 hydlu,ohoLic pl~ illg monomer having the general structure CH2C = COOR7 where R, is a straight chain or branched alkyl group having from 2 to 22 carbon atoms, and particularly is a plcali~ lg monomer selected from at least one of the group con;,;c,li"9 of 2-ethyl hexl acrylate, n-butyl acrylate and stearyl methacrylate.
The above ",~"lioned ,ula~ illg IIIOIIOIII~,.a are particularly suitable for use by illcol~Jola~i"g with the hyd,u~ul monomer before the mixture is polymerized. It is so",_~i",es desirable to partially polymerize 20 the hydrophilic ",ol,o",elic material, illcor~Jola~ a water soluble, relatively non-volatile iat room temperature) polyol in amounts of about 1 to about 20% iby weight), preferably about 3% to about 8% Iby weight). Suitable polyols include polyethylene glycol, polypropylene glycol and copoiymers of ethylene oxide and propylene oxide and glycerol. The copolymers of wos6l03l6.l 2 t 9~744 .~.,u~ .c~67 ethylene oxide and propylene oxide should be of the general formula HO(-CHaCHCH20-)m-lCH2CH20)n-CH2CH20H
where m and n are positive integers.
The invention is generally directed to a coating for an illLIacor~uult al device and particulariy to an e~JalldaiJI~ portion of intraluminal catheter such as the balloon on a dilatation catheter for coronary angioplasty. The dilatation catheters have an elongated catheter shaft with at least one inner lumen which is adapted to direct ;nflation liquid therethrough and an inflatable member or balloon on the distal extremity of the catheter shaft which has an interior in fluid communication with the inner lumen within the shaft. The inflatable member or balloon is adapted to dilate body lumens such as stenotic coronary and peripheral arteries, prostatic urethras and the like.
In a presently preferred ~ iJO-,i;.ll.,.~, the balloon material is a thGallùplaaLi1 polymer or a blend of Lllt,llllo~Jl.. ~.Li., polymers such as polyethylene, poltuLl,~l~..,e t~le~ullLllalaL~, polt.,Jt~.b (e.g. Nyloni and suitable ionomers.
The balloon of the invention is made by forming a tubular product cf the desired polymeric material using conventional melt 20 pluceba;"g techniques, such as extruding. hfter the tubular product of the desired co"".oaiLion is formed, it may be blown in a conventional fashion into a relatively inelastic balloon.
The polymers from which the balloon is made may be cross-linked by the use of a suitable cross-linking agent such as a peroxide or wo 96/03164 ~ 267 ~ an amine, or by illadiaLiOIl with gamma or eiectron beam radiation. It is plt:reldiJ!~ to ill~ol~Julale a cross linking agent in amounts ranging from about 0.1 to about 2 %, ~ dbly about 0.1 to about 1 Yo into the poiymer from which the balloon is made before it is formed to facilitate cross-linking upon ;~a i;aliL~n. Suitable cross-linking agents include CUIII~JOII~IIID having carbon-carbon unsaturation, e.g. ethylenic double bonds, such as allyl, methallyl, proparsyl or vinyl groups. Preferred cross linking agents include triallyl cyanurate, triallyl isocyanurate, triallyl Ll;lll " , triallyl 1,;", tetraallyl pyl.""~ .t~ and the diallyl ester of 1,1,3-trimethyl-5-carboxy-3-~p-carboxyphenyl) indane.
In one presently preferred method of forming the coating of the invention on the surface of the balloon on a dilatation catheter, the catheter is dipped into an aqueous solution cor,L~.;.,;"g about 0.5 to about 20~h (by wt.), preferably about 2 to about 7%, polymer solids, which includes the reacted copoly."el of the hyd,u~,l, ",ono",eric material and the plaDIi~ ;L;~I9 ,.,ono",elic material and an additional h~idl..pl polymer.
The catheter is dipped at a rate of about 5 to about 40 cm per minute.
Upon removal from the aqueous solution, the catheter is irradiated to cross link the polymeric coating material, e.g. ultraviolet radiation from a 20 mercury lamp for about 10 seconds to about 10 minutes at an intensity of about 5 to about 260 milliwatts, preferably about 10 to about 50 milliwatts, per cm2 of catheter surface.
The coating of the invention on the catheter surface, particularly the coating on the balloon, is quite durable, exhibits good ~ , ~ t ~o 96/03164 2 1 9 5 7 ~ ~ }~ ,267 flexibiiity and is .,halcl,,11,li~Od by very low coefficients of friction. As a result, the catheter can be readily advanced through guiding catheters and tortuous coronary anatomy. The coating also eases the passage of the balloon intG tight stenoses. These and other advantages of the invention will become more apparent from the following detailed dc~..li~JLi~,ll of the invention when taken in conjunction with the accor"~.,."~ri"g exemplary drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is an elevational view of an over-the-wire dilatation catheter tlllbo.Jy;.,g features of the invention.
DET,~" Fn DESCRIPTION OF THE INVENTJON
Fig. 1 illustrates a dilatation catheter lO which includes an elongated catheter shaft 11 cor,.~ i"g an inner tubular member 12 and an outer tubular member 13, a balloon or inflatable member 14 and an adapter 15. The inner tubular member 12 has an inner lumen 16 which is adapted to receive the guidewire 17 and defines with the QUter tubular member 13 an annular lumen 18 which is adapted to direct inflation fluid to the interior of the balloon 14. The arm 19 of the adapter 15 directs inflation fiuid from 8 source not shown into the annular lumen.
In the .""I,od;..,~ shown in the drawings, part of the shaft 11 and the balloon 14 are provided with a durable yet flexible hyJIOpll ' coating 20 in accordclllce with the present invention. In other wo ~6/03164 21 9 5 7 4 4 rul/~J. . C 26s a,.,l,o,' ,t:"Ls the balloon 14 alone may be provided with the flexible hydrophilic coating of the invention.
The dry coating thickness of the h~ u?ll ' - coating generally will range from about 0.00002 to about 0.001 inch 10.0005-0.025 mm~, p,t rt".lbly about 0.00005 to about 0.0005 inch 10.0013-0.013 mmi.
The materials of construction of the various catheter cor"~Jullt~ such as the inner tubular member 12 and the adapter 15 may be formed of cOll~l~.lliùllal materials, e.g. polyethylene, polyvinyl chloride, pol,ra".ida and the like. The means used to join the various catheter co",uon~"L:, may be conventional such as by heat or laser bonding, heat shrinking or use of a suitable adhesive. The various catheter co"i,uon~ will generally be of conventional size dc?e-,.li.,y upon the intended end use.
The following is a exampie of applying a coating to the distal portion of a balioon dilatation catheter for J.ly;o,bla~y procedures. The catheter surface was first cleaned with 2-propanol and plasma treated with oxygen to prepare the surface for optimal coating adhesion. The catheter was dipped into an aqueous bath COIIL~A~I ,9 3% polymer solids which includes about 50% of a first l"rd,u,ul, ' poiymer and about 50%
of a second hydrophilic polymer which is a copolymer of a hydrophilic monomer and a ula:,LiL;i~al monomer in accordsnce with the invention.
The bath was ", ,ad at a temperature of about 20-C. The catheter surface was then subjected to ultraviolet radiation from a mercury lamp at wo 96~03164 2 ~ ~ 5 7 4 4 r~ "e~ ~ 267 an intensity of 1 2 ~ l7 for about 3 minutes to cure the coating.
Two coats were appl;ed in essa.)tiJlly the same manner. The coating was found to be durable, very flexible and lubricous. When subjected to an aqueous based liquid, the coating had a coerriu;a.,L of friction of about 5 0.03. No cracks or d~ .,,;.,al;uns of the coating were noted.
The first l,~/d,u,ul "' polymer was a polymer material sold by the Bio-Metric Systems, Inc. (BSI), under ths de~iyllaliun PV05 which is a polymer primarily formed of n-vinyl pyrrolidone. The polymer material as sold had been treated to attach latent photoactive groups to facilitate the 10 bonding of the reacted polymer to the desired substrate, as taught in U.S.
Patent 5,002,582 and the other patent i"co,~uore..~,d by reference. The second hyd,uul.''' polymer was a polymer material sold by BSI under the dac:~"bliu" PA05 which is a polymer primarily formed of acl yla~ll;dd, but which included 7.2% methoxy pu~ glycol (1000 mol. wt.) mono methacrylate (Methoxy PEG 1000 MMA). The second polymer as sold had likewise been treated to attach latent pl,uLua~ e groups to facilitate the bonding of the reacted polymer to the desired substrate as previously described.
In another example, a 3% polymer solids bath was prepared co, Il.A;.Iillg 1.5% PVQ5 and 1.5% PA03 which is the same as PA05 but without the Methoxy PEti 1000 MMa pla~ lg monomer. A coating was prepared on the balloon of a dilatation catheter in the same manner as in the previous example. The dry, cured coating formed cracks and some coating segments d~ .ll;,laltd from the underlying balloon surface o ~6103164 ~ ,267 which pvL~ Li~lly can reduce pe, ru""a"-,e and result in in-vivo particle gene. a Liuu.
While the detailed ds__ii,uL;ùll of the invention has been described herein in terms of a presently preferred e".i _ ' "a.,l con",,i~i"g a balloon dilatation catheter for PTCA, those skiiled in the art will recognize that the coating of the invention may be employed in a wide variety of devices in contact with various body fluids both i"ll.,.,o",u,t:ally and ~ a~ol~uun~lly~ For example, the coating may be utilized on catheters adapted to dilate prostatic urethras and other body lumens and the coating can be utilized on dialysis machines. Likewise, other ~aliùns and improvements may be made to the present invention without departing from the scope of the invention.
.
HYDROPHILIC COATING MATERIAL
FOR INTRACORrCiRtAL USE
BACKGROUND OF THE INVENTION
This invention generally relates to intraluminal catheters, such as guiding catheters and balloon dilatation catheters used in percutaneous transluminal coronary ally;Oplac~ly IPTCA).
In typical PTCA procedures, a guiding catheter having a p~ ha~Jed distal tip is percutaneously introduced by a Seldinger technique into the cardiovascular system of a patient and advanced within the system until the pl~ llalJcd distal tip of the guiding catheter is disposed ~ within the ascen " lg aorta adjacent the ostium of the desired coronary artery. The guiding catheter is twisted or torqued from its proximal end, which extends outside the patient, to turn the distal tip of the guiding catheter so that it can be guided into the desired coronary ostium. A
balloon dilatation catheter are introduced into and advanced through the guiding catheter to the distal tip thereof out of the distal tip of~ the guiding WO~6~03164 ' 2~1 9 5 7 ~ 4 r~ 3267 catheter until the balioon on the distal extremity of the dilatation catheter--is properly poviliuned across the lesion. Once properly poD;Iiuncd, the balloon is inflated to a p,~,d~ .llli"ed size with r~ .paq~e liquid at relatively high pressures (e.g., generally ~12 aLlllu.pll_,~s) to dilate the stenotic region of the diseased artery. One or more inflations may be necessary to effectively dilate the stenosis. Additional stenoses may be dilatated with the same catheter. When the dilala~iùns are col"ul~ltsd, the balloon is deflated so that the dilatation catheter can be removed from the dilated stenosis and normal blood fiow will resume through the dilated 1 0 artery.
There are several well known types of balloon dilatation catheters which are suitable for coronary a"v, ' :y. They include conventional over-the-wire catheters, fixed-wire catheters, rapid exchange type catheters and perfusion type catheters.
Lubricous coatings have been applied to the surfaces of guiding catheters, dilatation catheters and other intraluminal catheters in order to reduce the coerri,,;_." of friction of the surfaces of these catheters and to facilitate the adva"ccl."~ and v.;ll,d,~.a: of these catheters through various body lumens. For example, silicone coatings have been applied to the exterior of various catheters in order to reduce the coerri~ .,l of friction of the catheter surface, but these coatings are frequently not very durable and lose substantial portions of their lubricity during an intraluminal or intravascular procedure. Durable, lubricous silicone coatings are described in cope.,d;.,g r, 1''-~ Serial No.
WO g6/0316~ 2 1 9 ~ 7 4 4 PcrlussSIOg267 ~ 071913,775, filsd July 13, 1992, but the 8,), '- .- of these lubricous coatings and linings described in the copen ' Iy . r ~ ~ are for the most part co", ' ' manufacturing procedures.
What has been needed and h.,.~Luru~e IJ"~.. ' ' ' is a durable coating for plastic surfaces having long lasting lubricity which does not require cGr", ' ' manufacturing procedures. The present invention satisfies this and other needs.
SUMMARY OF THE INVENTIQN
This invention is directed to an improved i"l".cor~.o,eal device, such as a cathetsr, having a durable, flexible coating which is formed of hyd,ù~Jl 'i~ material and which provides a low COérriuiélll of friction when in contact with an aqueous based liquid.
The durable, flexible coating of the invention is generally formed at least in part from a cOpol,/."e, product co"",,i,i"g a hydrophilic ",onc.",è,ic material and a pl~Li~;iLillg ~"onor"e,i~; material. The copolymer product cu",~u,iaas at least about 50% of the h~/dlopl ' -monomer and from about 2~h to about 50Yo, IJIere,clLly about 5~h to about 30~h, of the plt.;.Li~.i.;,lg monomer. As used herein, all l~f~,.enc to percent refer to percent by weight unless otherwise noted. The co-polymer is treated to attach latent photoactive groups to facilitate the bonding of the reacted copolymer to the desired substrate, as taught in U.S. Patent 5,002,582, which is illcol,uolt~Led herein by reference.
Additional disclosures are found in U.S. Patent 4,722,906, U.S. Patent 4,973,493 and U.S. Patent 4,979,959 which are i,,cor~,u,aLed herein by wo 9CI03164 2 1 9 5 7 4 4 1~ S ~.'C Lti7 reference. The coating formed is a durable, flexible h,/J-opl~ " coating.
At least about 30%r p,ef~,.di,ly at least about 40%, of the coatins should comprise the copolymer of the htd~uul. ' monomer and the plaali~ g monomer. Other i-,y.l,u~Jl ' polymers may be illcul,uOIal~d into the coating to modify coating ,u.ope.li__. The additional hydrophilic polymers should likewise be treated to attach latent,ul,otua~Lie groups as previously described.
The hydrophilic ~u~vlll~ , material forming the copolymer and the hyl.upl ' I"ol,or,l.,lic material forming any hydrophilic polymer illcol~,olc,L~;.l into the coating with the copol~"._. are pltiFe.dbl; seiected from one or more h,~d,upi, ' ",uno,.w,:, having the general formula R,CH = CR2R3 where R, is a hydrogen or pyrrolidone, R2 is a hydrogen or a methyl group, R3 is a hydrogen or -COR", and R~ is -NH2r -OH, -NHC(CH3)2CH2COF,5, -NICH3)2, -OlCH2)nOH, or-OCH3CHCH20H, where Rs is CH3 or OH, and nis1 or2 Particularly suitable ~/dlu,ul ' ulOI-OIIl~la include acrylamide and N-vinyl pyrrolidone.
The ,ulaaLi~ l may be a l~/lluph' plaaLiuia;llg monomer and particularly a pla~ i,lg monomer having the general formula CH2 = CR6-coolcH2cH2o)ncH2cH2oRs WO 96/03164 1 ~ IIIJ,.,~.. ~J~67 ~ where R6 is a hydrogen or methyl group and n is an integer from about 1 to about 25.
A suitable l-.yd,u,ul, " ple.~liLi~;ll9 monomer may at least in part be selected from the group con;.;~li"g of Imethoxy)polylethylene 5 glycol) ",ono",~ll,a- ,ylate, poly(ethylene glycol) Illonolllcllla~ l..t~, Imethoxy)poly(ethylene glycol) acrylate, polyjethylene glycol) acrylate, having a molecular weight from about 500 to about 1500, and mixtures thereof.
The pla~ material may also be at least in part a ~0 hydlu,ohoLic pl~ illg monomer having the general structure CH2C = COOR7 where R, is a straight chain or branched alkyl group having from 2 to 22 carbon atoms, and particularly is a plcali~ lg monomer selected from at least one of the group con;,;c,li"9 of 2-ethyl hexl acrylate, n-butyl acrylate and stearyl methacrylate.
The above ",~"lioned ,ula~ illg IIIOIIOIII~,.a are particularly suitable for use by illcol~Jola~i"g with the hyd,u~ul monomer before the mixture is polymerized. It is so",_~i",es desirable to partially polymerize 20 the hydrophilic ",ol,o",elic material, illcor~Jola~ a water soluble, relatively non-volatile iat room temperature) polyol in amounts of about 1 to about 20% iby weight), preferably about 3% to about 8% Iby weight). Suitable polyols include polyethylene glycol, polypropylene glycol and copoiymers of ethylene oxide and propylene oxide and glycerol. The copolymers of wos6l03l6.l 2 t 9~744 .~.,u~ .c~67 ethylene oxide and propylene oxide should be of the general formula HO(-CHaCHCH20-)m-lCH2CH20)n-CH2CH20H
where m and n are positive integers.
The invention is generally directed to a coating for an illLIacor~uult al device and particulariy to an e~JalldaiJI~ portion of intraluminal catheter such as the balloon on a dilatation catheter for coronary angioplasty. The dilatation catheters have an elongated catheter shaft with at least one inner lumen which is adapted to direct ;nflation liquid therethrough and an inflatable member or balloon on the distal extremity of the catheter shaft which has an interior in fluid communication with the inner lumen within the shaft. The inflatable member or balloon is adapted to dilate body lumens such as stenotic coronary and peripheral arteries, prostatic urethras and the like.
In a presently preferred ~ iJO-,i;.ll.,.~, the balloon material is a thGallùplaaLi1 polymer or a blend of Lllt,llllo~Jl.. ~.Li., polymers such as polyethylene, poltuLl,~l~..,e t~le~ullLllalaL~, polt.,Jt~.b (e.g. Nyloni and suitable ionomers.
The balloon of the invention is made by forming a tubular product cf the desired polymeric material using conventional melt 20 pluceba;"g techniques, such as extruding. hfter the tubular product of the desired co"".oaiLion is formed, it may be blown in a conventional fashion into a relatively inelastic balloon.
The polymers from which the balloon is made may be cross-linked by the use of a suitable cross-linking agent such as a peroxide or wo 96/03164 ~ 267 ~ an amine, or by illadiaLiOIl with gamma or eiectron beam radiation. It is plt:reldiJ!~ to ill~ol~Julale a cross linking agent in amounts ranging from about 0.1 to about 2 %, ~ dbly about 0.1 to about 1 Yo into the poiymer from which the balloon is made before it is formed to facilitate cross-linking upon ;~a i;aliL~n. Suitable cross-linking agents include CUIII~JOII~IIID having carbon-carbon unsaturation, e.g. ethylenic double bonds, such as allyl, methallyl, proparsyl or vinyl groups. Preferred cross linking agents include triallyl cyanurate, triallyl isocyanurate, triallyl Ll;lll " , triallyl 1,;", tetraallyl pyl.""~ .t~ and the diallyl ester of 1,1,3-trimethyl-5-carboxy-3-~p-carboxyphenyl) indane.
In one presently preferred method of forming the coating of the invention on the surface of the balloon on a dilatation catheter, the catheter is dipped into an aqueous solution cor,L~.;.,;"g about 0.5 to about 20~h (by wt.), preferably about 2 to about 7%, polymer solids, which includes the reacted copoly."el of the hyd,u~,l, ",ono",eric material and the plaDIi~ ;L;~I9 ,.,ono",elic material and an additional h~idl..pl polymer.
The catheter is dipped at a rate of about 5 to about 40 cm per minute.
Upon removal from the aqueous solution, the catheter is irradiated to cross link the polymeric coating material, e.g. ultraviolet radiation from a 20 mercury lamp for about 10 seconds to about 10 minutes at an intensity of about 5 to about 260 milliwatts, preferably about 10 to about 50 milliwatts, per cm2 of catheter surface.
The coating of the invention on the catheter surface, particularly the coating on the balloon, is quite durable, exhibits good ~ , ~ t ~o 96/03164 2 1 9 5 7 ~ ~ }~ ,267 flexibiiity and is .,halcl,,11,li~Od by very low coefficients of friction. As a result, the catheter can be readily advanced through guiding catheters and tortuous coronary anatomy. The coating also eases the passage of the balloon intG tight stenoses. These and other advantages of the invention will become more apparent from the following detailed dc~..li~JLi~,ll of the invention when taken in conjunction with the accor"~.,."~ri"g exemplary drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is an elevational view of an over-the-wire dilatation catheter tlllbo.Jy;.,g features of the invention.
DET,~" Fn DESCRIPTION OF THE INVENTJON
Fig. 1 illustrates a dilatation catheter lO which includes an elongated catheter shaft 11 cor,.~ i"g an inner tubular member 12 and an outer tubular member 13, a balloon or inflatable member 14 and an adapter 15. The inner tubular member 12 has an inner lumen 16 which is adapted to receive the guidewire 17 and defines with the QUter tubular member 13 an annular lumen 18 which is adapted to direct inflation fluid to the interior of the balloon 14. The arm 19 of the adapter 15 directs inflation fiuid from 8 source not shown into the annular lumen.
In the .""I,od;..,~ shown in the drawings, part of the shaft 11 and the balloon 14 are provided with a durable yet flexible hyJIOpll ' coating 20 in accordclllce with the present invention. In other wo ~6/03164 21 9 5 7 4 4 rul/~J. . C 26s a,.,l,o,' ,t:"Ls the balloon 14 alone may be provided with the flexible hydrophilic coating of the invention.
The dry coating thickness of the h~ u?ll ' - coating generally will range from about 0.00002 to about 0.001 inch 10.0005-0.025 mm~, p,t rt".lbly about 0.00005 to about 0.0005 inch 10.0013-0.013 mmi.
The materials of construction of the various catheter cor"~Jullt~ such as the inner tubular member 12 and the adapter 15 may be formed of cOll~l~.lliùllal materials, e.g. polyethylene, polyvinyl chloride, pol,ra".ida and the like. The means used to join the various catheter co",uon~"L:, may be conventional such as by heat or laser bonding, heat shrinking or use of a suitable adhesive. The various catheter co"i,uon~ will generally be of conventional size dc?e-,.li.,y upon the intended end use.
The following is a exampie of applying a coating to the distal portion of a balioon dilatation catheter for J.ly;o,bla~y procedures. The catheter surface was first cleaned with 2-propanol and plasma treated with oxygen to prepare the surface for optimal coating adhesion. The catheter was dipped into an aqueous bath COIIL~A~I ,9 3% polymer solids which includes about 50% of a first l"rd,u,ul, ' poiymer and about 50%
of a second hydrophilic polymer which is a copolymer of a hydrophilic monomer and a ula:,LiL;i~al monomer in accordsnce with the invention.
The bath was ", ,ad at a temperature of about 20-C. The catheter surface was then subjected to ultraviolet radiation from a mercury lamp at wo 96~03164 2 ~ ~ 5 7 4 4 r~ "e~ ~ 267 an intensity of 1 2 ~ l7 for about 3 minutes to cure the coating.
Two coats were appl;ed in essa.)tiJlly the same manner. The coating was found to be durable, very flexible and lubricous. When subjected to an aqueous based liquid, the coating had a coerriu;a.,L of friction of about 5 0.03. No cracks or d~ .,,;.,al;uns of the coating were noted.
The first l,~/d,u,ul "' polymer was a polymer material sold by the Bio-Metric Systems, Inc. (BSI), under ths de~iyllaliun PV05 which is a polymer primarily formed of n-vinyl pyrrolidone. The polymer material as sold had been treated to attach latent photoactive groups to facilitate the 10 bonding of the reacted polymer to the desired substrate, as taught in U.S.
Patent 5,002,582 and the other patent i"co,~uore..~,d by reference. The second hyd,uul.''' polymer was a polymer material sold by BSI under the dac:~"bliu" PA05 which is a polymer primarily formed of acl yla~ll;dd, but which included 7.2% methoxy pu~ glycol (1000 mol. wt.) mono methacrylate (Methoxy PEG 1000 MMA). The second polymer as sold had likewise been treated to attach latent pl,uLua~ e groups to facilitate the bonding of the reacted polymer to the desired substrate as previously described.
In another example, a 3% polymer solids bath was prepared co, Il.A;.Iillg 1.5% PVQ5 and 1.5% PA03 which is the same as PA05 but without the Methoxy PEti 1000 MMa pla~ lg monomer. A coating was prepared on the balloon of a dilatation catheter in the same manner as in the previous example. The dry, cured coating formed cracks and some coating segments d~ .ll;,laltd from the underlying balloon surface o ~6103164 ~ ,267 which pvL~ Li~lly can reduce pe, ru""a"-,e and result in in-vivo particle gene. a Liuu.
While the detailed ds__ii,uL;ùll of the invention has been described herein in terms of a presently preferred e".i _ ' "a.,l con",,i~i"g a balloon dilatation catheter for PTCA, those skiiled in the art will recognize that the coating of the invention may be employed in a wide variety of devices in contact with various body fluids both i"ll.,.,o",u,t:ally and ~ a~ol~uun~lly~ For example, the coating may be utilized on catheters adapted to dilate prostatic urethras and other body lumens and the coating can be utilized on dialysis machines. Likewise, other ~aliùns and improvements may be made to the present invention without departing from the scope of the invention.
Claims (31)
1. A flexible hydrophilic coating comprising the reaction product of:
a) a hydrophilic monomer; and b) a plasticizer monomer.
a) a hydrophilic monomer; and b) a plasticizer monomer.
2. The hydrophilic coating of claim 1 wherein the reaction product includes at least about 50% of hydrophilic monomer and from about 5 to about 50% of plasticizer monomer.
3. The hydrophilic coating of claim 1 wherein the hydrophilic monomer has the formula R1CH = CR2R3 where R1 is a hydrogen or pyrrolidone, R2 is a hydrogen or a methyl group, R3 is a hydrogen or -COR4, and R4 is -NH2, -OH, -NHC(CH3)2CH2COR5, -N(CH3)2, -O(CH2)nOH, or-OCH3CHCH2OH, where R5 is CH3 or OH, and n is 1 or 2
4. The coating of claim 1 wherein the plasticizer monomer is hydrophilic.
5. The coating of claim 2 wherein the hydrophilic plasticizer monomer has the formula CH2=CR6-COO(CH2CH2O)nCH2CH2OR8 where R6 is a hydrogen or methyl group.
6. The coating of claim 3 wherein the hydrophilic plasticizer monomer is selected from at least one of the group consisting of methoxy poly(ethylene glycol) monomethacrylate, poly(ethylene glycol) monomethacrylate, methoxy poly(ethylene glycol) acrylate and poly(ethylene glycol) acrylate.
7. The coating of claim 6 wherein the selected hydrophilic plasticizer monomer has a molecular weight from about 500 to about 1500.
8. The coating of claim 1 wherein the plasticizer monomer is a hydrophobic plasticizer having the general formula CH2C = COOR5 where R5 is a straight chain or branched alkyl group having from 2 to 22 carbon atoms.
9. The coating of claim 8 wherein the plasticizer monomer is selected from at least one of the group consisting of 2-ethyl hexl acrylate, n-butyl acrylate and stearyl methacrylate.
10. The flexible hydrophilic coating of claim 1 wherein the hydrophilic monmeric material is partially polymerized with the plasticizer monomer and then a water soluble, relatively non-volatile polyol in an amount of about 1 to about 20% is incorporated into the partially polymerized monomeric material.
11. The flexible hydrophilic coating of claim 1 wherein the hydrophilic monmeric material is partially polymerize with the plasticizer monomer and then a water soluble, relatively non-volatile polyol in amounts of about 3 to about 8% are incorporated into the partially polymerized monomeric material.
12. The flexible hydrophilic coating of claim 10 wherein the polyol is selected from one or more of the group consisting of polyethyleno glycol, polypropylene glycol and copolymers of ethylene oxide and propylene oxide and glycerol.
13. The hydrophilic coating of claim 12 wherein the copolymers of ethylene oxide and propylene oxide have the general formula HO(-CH3CHCH2O-)m-(CH2CH2O)n-CH2CH2OH
where m and n are positive integers.
where m and n are positive integers.
14. The hydrophilic coating of claim 1 wherein the copolymer comprises at least 30% of the components thereof.
15. The hydrophilic coating of claim 1 wherein the copolymer comprises at least 40% of the components thereof.
16. The hydrophilic coating of claim 15 including up to 50% of one or more additional hydrophilic polymers.
17. An intraluminal catheter having a flexible hydrophilic coating at least on an exterior portion thereof which comprises:
a) at least about 50% by weight of a hydrophilic monomer having the formula R1CH=CR2R3 where R1 is a hydrogen or pyrrolidone, R2 is a hydrogen or a methyl group, R3 is a hydrogen or -COR4, and R4 is -NH2, -OH, -NHC(CH3)2CH2COR5, -N(CH3)2, -O(CH2)nOH, or -OCH3CHCH2OH, where R5 is CH3 or OH, and n is 1 or 2; and b) from about 5 to about 50% of a plasticizer monomer.
a) at least about 50% by weight of a hydrophilic monomer having the formula R1CH=CR2R3 where R1 is a hydrogen or pyrrolidone, R2 is a hydrogen or a methyl group, R3 is a hydrogen or -COR4, and R4 is -NH2, -OH, -NHC(CH3)2CH2COR5, -N(CH3)2, -O(CH2)nOH, or -OCH3CHCH2OH, where R5 is CH3 or OH, and n is 1 or 2; and b) from about 5 to about 50% of a plasticizer monomer.
18. The intraluminal catheter of claim 17 wherein the plasticizer is a hydrophilic plasticizer.
19. The intraluminal catheter of claim 18 wherein the hydrophilic plasticizer is CH2 = CR6-COO(CH2CH2O)nCH2CH2OH
where R6 is a hydrogen or methyl group.
where R6 is a hydrogen or methyl group.
20. The intraluminal catheter of claim 17 wherein the hydrophilic plasticizer is selected from one or more of the group consisting of methoxy poly(ethylene glycol) monomethacrylate, poly(ethylene glycol) monomethacrylate, methoxy poly(ethylene glycol) acrylate and poly(ethylene glycol) acrylate.
21. The intraluminal catheter of claim 20 wherein the selected hydrophilic plasticizer has a molecular weight from about 500 to about 1500.
22. The intraluminal catheter of claim 17 wherein the plasticizer material is at least in part a hydrophilic plasticizer having the general formula CH2C = COOR5 where R5 is a straight chain or branched alkyl group having from 2 to 22 carbon atoms.
23. The intraluminal catheter of claim 22 wherein the hydrophilic plasticizer is selected from at least one of the group consisting of 2-ethyl hexl acrylate, n-butyl acrylate and stearyl methacrylate.
24. In a balloon dilatation catheter having an elongated shaft and an inflatable dilatation member on a distal portion of the elongated shaft, the improvement comprising a hydrophilic coating on at least the exterior of the balloon which comprises the reaction product of:
a) at least about 50% by weight of a hydrophilic monomer having the formula R1CH = CR2R3 where R1 is a hydrogen or pyrrolidone, R2 is a hydrogen or a methyl group, R3 is a hydrogen or -COR4, and R4 is -NH2, -OH, -NHC(CH3)2CH2COR5, -N(CH3)2, -O(CH2)nOH, or-OCH3CHCH2OH, where R5 is CH3 or OH, and n is 1 or 2; and b) from about 5 to about 50% of a hydrophilic plasticizer monomer having the formula CH2 = CR6-COO(CH2CH2O)nCH2CH2OH
where R6 is a hydrogen or methyl group.
a) at least about 50% by weight of a hydrophilic monomer having the formula R1CH = CR2R3 where R1 is a hydrogen or pyrrolidone, R2 is a hydrogen or a methyl group, R3 is a hydrogen or -COR4, and R4 is -NH2, -OH, -NHC(CH3)2CH2COR5, -N(CH3)2, -O(CH2)nOH, or-OCH3CHCH2OH, where R5 is CH3 or OH, and n is 1 or 2; and b) from about 5 to about 50% of a hydrophilic plasticizer monomer having the formula CH2 = CR6-COO(CH2CH2O)nCH2CH2OH
where R6 is a hydrogen or methyl group.
25. The dilatation catheter of claim 24 wherein the hydrophilic plasticizer is selected from one or more of the group consisting of methoxy poly(ethylene glycol) monomethacrylate, poly(ethylene glycol) monomethacrylate, methoxy poly(ethylene glycol) acrylate and poly(ethylene glycol) acrylate.
26. The dilatation catheter of claim 25 wherein the selected hydrophilic plasticizer has a molecular weight from about 500 to about 1500.
27. The dilatation catheter of claim 24 wherein the copolymer comprises at least 30% of the coating.
28. The dilatation catheter of claim 24 wherein the copolymer comprises at least 40% of the coating.
29. The dilatation catheter of claim 28 wherein the coating includes up to 50% at least one additional hydrophilic polymers.
30. The dilatation catheter of claim 24 wherein the copolymer is bonded to the balloon by means of latent photoactive groups.
31. The dilatation catheter of claim 29 wherein the additional hydrophilic polymer is n-vinyl pyrrolidone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US27923994A | 1994-07-22 | 1994-07-22 | |
| US08/279239 | 1994-07-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2195744A1 true CA2195744A1 (en) | 1996-02-08 |
Family
ID=23068189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2195744 Abandoned CA2195744A1 (en) | 1994-07-22 | 1995-07-21 | Hydrophilic coating material for intracorporeal use |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0772467A1 (en) |
| JP (1) | JP2000511946A (en) |
| CA (1) | CA2195744A1 (en) |
| WO (1) | WO1996003164A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455500B1 (en) | 1998-03-10 | 2002-09-24 | University Of Southern California | Radiation therapy methods |
| US5998534A (en) * | 1998-06-19 | 1999-12-07 | Ppg Industries Ohio, Inc. | Water-soluble or water-dispersible addition copolymer |
| JP4602556B2 (en) * | 1998-11-20 | 2010-12-22 | コロプラスト アクティーゼルスカブ | Method for sterilizing medical devices having a hydrophilic coating |
| US7030203B2 (en) | 2001-09-28 | 2006-04-18 | 3M Innovative Properties Company | Water-in-oil emulsions with ethylene oxide groups, compositions, and methods |
| US6951642B2 (en) | 2001-09-28 | 2005-10-04 | 3M Innovative Properties Company | Water-in-oil emulsions with anionic groups, compositions, and methods |
| US7097850B2 (en) | 2002-06-18 | 2006-08-29 | Surmodics, Inc. | Bioactive agent release coating and controlled humidity method |
| US20040111144A1 (en) * | 2002-12-06 | 2004-06-10 | Lawin Laurie R. | Barriers for polymeric coatings |
| GB2448871A (en) * | 2007-04-30 | 2008-11-05 | Inion Ltd | Modulation of inflammatory and immune responses in the treatment of inflammation using substituted heterocyclic compounds |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3566874A (en) * | 1968-08-13 | 1971-03-02 | Nat Patent Dev Corp | Catheter |
| US4055682A (en) * | 1971-11-19 | 1977-10-25 | High Voltage Engineering Corporation | Catheter and the method of making |
| AU494547B2 (en) * | 1972-07-10 | 1977-10-20 | Johnson & Johnson | Hydrophilic random interpolymer compositions and method for making same |
| SE448544B (en) * | 1979-12-05 | 1987-03-02 | Kendall & Co | WATER ABSORPTION COMPOSITION AND USE THEREOF AS A CARRIER FOR A MEDICINE |
| US4373009A (en) * | 1981-05-18 | 1983-02-08 | International Silicone Corporation | Method of forming a hydrophilic coating on a substrate |
| GB8611838D0 (en) * | 1986-05-15 | 1986-06-25 | Yarsley Technical Centre Ltd | Hydrophilic copolymers |
| EP0389632A4 (en) * | 1988-08-09 | 1990-12-27 | Toray Industries, Inc. | Slippery medical material and process for its production |
| EP0521605A3 (en) * | 1991-05-16 | 1993-03-10 | Ioptex Research Inc. | Biocompatible lubricious grafts |
| US5531715A (en) * | 1993-05-12 | 1996-07-02 | Target Therapeutics, Inc. | Lubricious catheters |
-
1995
- 1995-07-21 CA CA 2195744 patent/CA2195744A1/en not_active Abandoned
- 1995-07-21 JP JP08505890A patent/JP2000511946A/en active Pending
- 1995-07-21 EP EP95928107A patent/EP0772467A1/en not_active Ceased
- 1995-07-21 WO PCT/US1995/009267 patent/WO1996003164A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996003164A1 (en) | 1996-02-08 |
| EP0772467A1 (en) | 1997-05-14 |
| JP2000511946A (en) | 2000-09-12 |
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