US20150018431A1 - Lubricious Coating Compositions - Google Patents
Lubricious Coating Compositions Download PDFInfo
- Publication number
- US20150018431A1 US20150018431A1 US14/330,734 US201414330734A US2015018431A1 US 20150018431 A1 US20150018431 A1 US 20150018431A1 US 201414330734 A US201414330734 A US 201414330734A US 2015018431 A1 US2015018431 A1 US 2015018431A1
- Authority
- US
- United States
- Prior art keywords
- coating composition
- lubricous coating
- pvp
- molecular weight
- agents
- 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
- 239000008199 coating composition Substances 0.000 title claims abstract description 41
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 81
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 81
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 61
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical group C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 23
- -1 acrylate compound Chemical class 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 8
- 239000003814 drug Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229940124597 therapeutic agent Drugs 0.000 claims description 4
- 208000004434 Calcinosis Diseases 0.000 claims description 2
- 230000002769 anti-restenotic effect Effects 0.000 claims description 2
- 239000003146 anticoagulant agent Substances 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims description 2
- 239000002246 antineoplastic agent Substances 0.000 claims description 2
- 229960004676 antithrombotic agent Drugs 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims description 2
- 230000002308 calcification Effects 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 67
- 239000002245 particle Substances 0.000 description 18
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 14
- 239000011877 solvent mixture Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 230000002792 vascular Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229940069328 povidone Drugs 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 229920003081 Povidone K 30 Polymers 0.000 description 2
- 229920003082 Povidone K 90 Polymers 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920006219 poly(vinylidene fluoride-co-hexafluoropropene) Polymers 0.000 description 2
- 229920000307 polymer substrate Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 description 1
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JEXYCADTAFPULN-UHFFFAOYSA-N 1-propylsulfonylpropane Chemical compound CCCS(=O)(=O)CCC JEXYCADTAFPULN-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- QKTWWGYCVXCKOJ-UHFFFAOYSA-N 2-methoxy-1-(2-methoxyphenyl)-2-phenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1OC QKTWWGYCVXCKOJ-UHFFFAOYSA-N 0.000 description 1
- OCLCRYNZYRSURW-UHFFFAOYSA-N 2-phenyl-2,3-dihydroinden-1-one Chemical compound C1C2=CC=CC=C2C(=O)C1C1=CC=CC=C1 OCLCRYNZYRSURW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000012958 Amine synergist Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 201000008450 Intracranial aneurysm Diseases 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 229920003072 Plasdone™ povidone Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920003078 Povidone K 12 Polymers 0.000 description 1
- 229920003079 Povidone K 17 Polymers 0.000 description 1
- 229920003080 Povidone K 25 Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 230000002490 cerebral effect Effects 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920006147 copolyamide elastomer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- QONGECDDDTYBGS-UHFFFAOYSA-N dimorpholin-4-ylmethanone Chemical compound C1COCCN1C(=O)N1CCOCC1 QONGECDDDTYBGS-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 210000003709 heart valve Anatomy 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002107 myocardial effect Effects 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- HLXZNVUGXRDIFK-UHFFFAOYSA-N nickel titanium Chemical compound [Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni] HLXZNVUGXRDIFK-UHFFFAOYSA-N 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UKASIOIEWZDBIT-UHFFFAOYSA-N phenyl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)C1=CC=CC=C1 UKASIOIEWZDBIT-UHFFFAOYSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229940100487 povidone k25 Drugs 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/40—Lubricating compositions characterised by the base-material being a macromolecular compound containing nitrogen
- C10M107/42—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- 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
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/10—Materials for lubricating medical devices
Definitions
- the present invention pertains to lubricous coating compositions that comprise (a) a higher molecular weight polyvinylpyrrolidone (also referred to herein as higher MW PVP), (b) a lower molecular weight polyvinylpyrrolidone (also referred to herein as lower MW PVP), and (c) a polyfunctional unsaturated crosslinking agent.
- a higher molecular weight polyvinylpyrrolidone also referred to herein as higher MW PVP
- a lower molecular weight polyvinylpyrrolidone also referred to herein as lower MW PVP
- a polyfunctional unsaturated crosslinking agent also referred to herein as higher MW PVP
- such lubricous coating compositions are present in crosslinked form on the surface of a medical article.
- the lubricous coating compositions further comprise a solvent.
- Such compositions may be, for example, applied to a substrate in the form of a layer and subsequently crosslinked, thereby forming a lubricious coating on the substrate.
- the present invention is directed to methods for forming various medical articles.
- An advantage of the present invention is that coatings can be provided which are both lubricious and durable. Another advantage of the present invention is that coatings can be provided which produce very low levels of particulates when in contact with aqueous fluids.
- FIG. 1 is a plot of frictional force (g) vs. number of friction cycles for different grades of PVP.
- FIG. 2 is a plot of frictional force (g) vs. number of friction cycles for different ratios of higher MW PVP to lower MW PVP.
- FIG. 3 is a plot of relative particle count (>10 micrometer) as a function of different ratios of higher MW PVP to lower MW PVP.
- FIG. 4 is a plot of relative particle count (>50 micrometer) as a function of different ratios of higher MW PVP to lower MW PVP.
- FIG. 5 is a plot of frictional force (g) vs. number of friction cycles for different overall solids content.
- FIG. 6 is a plot of relative particle count (>10 micrometer) as a function of overall solids content.
- FIG. 7 is a plot of relative particle count (>50 micrometer) as a function of overall solids content.
- FIG. 8 is a plot of frictional force (g) vs. number of friction cycles for different ratios of PVP to NPGDA.
- FIG. 9 is a plot of relative particle count (>50 micrometer) as a function of different ratios of PVP to NPGDA.
- the present disclosure pertains to lubricous coating compositions for various articles.
- the compositions comprise a mixture of a higher molecular weight polyvinylpyrrolidone (higher MW PVP) and a lower molecular weight polyvinylpyrrolidone (lower MW PVP) as well as a crosslinking agent.
- the K-value is a function of the average degree of polymerization and intrinsic viscosity of a given polymer and is calculated from the kinematic viscosity of a 1% w/v aqueous solution of the polymer.
- a higher MW PVP is defined as one having a K-value between 60 and 95 (e.g., ranging from 60 to 65 to 70 to 75 to 80 to 85 to 90 to 95). This corresponds to a weight average molecular weight between approximately 100,000 and 1,300,000. In preferred embodiments, the higher MW PVP will have a K-value between 85 and 95.
- a lower MW PVP is defined as one having a K-value between 5 and 35 (e.g., ranging from 5 to 10 to 15 to 20 to 25 to 30 to 35). This corresponds to a weight average molecular weight between approximately 2,000 and 95,000. In preferred embodiments, the lower MW PVP will have a K-value between 15 and 32.
- polyvinylpyrrolidone materials useful in the present disclosure include Povidone K12, Povidone K15, Povidone K17, Povidone K25, Povidone K30, Povidone K60, Povidone K90 and Povidone K120, among others.
- Polyvinylpyrrolidone is available from BASF Corp, Parsippany, N.J., USA under the tradenames Kollidon® and Luvitec® and from Ashland Inc., Halethorpe, Md., USA as Plasdone®.
- the crosslinking agent may be substantially uncrosslinked (degree of crosslinking less than 5%), partially crosslinked (degree of crosslinking between 5% and 95%), or substantially completely crosslinked (degree of crosslinking greater than 99%.
- the degree of crosslinking may range from 1% or less to 2% to 5% to 10% to 25% to 50% to 75% to 90% to 95% to 98% to 99% or more.
- the lubricous coating compositions are present on the surface of a medical article in solid form, with the crosslinking agent being at least partially crosslinked.
- the lubricous coating compositions are present in liquid form, with the crosslinking agent being substantially uncrosslinked.
- Such compositions may be, for example, applied to a substrate in the form of a layer and then at least partially crosslinked, thereby forming a lubricious coating on the substrate.
- such compositions comprise a solvent, which may be removed before, during and/or after a crosslinking step.
- Polyfunctional ethylenically unsaturated monomers are preferred as crosslinking agents.
- the polyfunctional ethylenically unsaturated monomers are compounds, including monomeric and oligomeric compounds, that have a two or more ethylenically unsaturated groups thereon that may be readily polymerized by a radical mechanism to form a polymer. Typically, such compounds have a number average of about 5000 or less, more typically about 1000 or less.
- Suitable polyfunctional ethylenically unsaturated monomers include di- and tri-functional acrylate and methacrylate compounds, collectively referred to as (meth)acrylate compounds, including (meth)acrylate esters, as well as divinyl and trivinyl compounds.
- polyfunctional ethylenically unsaturated monomers that may be used in the compositions of the present disclosure include neopentyl glycol di(meth)acrylates, including neopentyl glycol diacrylate (NPGDA), ethylene glycol di(meth)acrylates, 1,3-propylene glycol di(meth)acrylates, 1,4-butanediol di(meth)acrylates, 1,6-hexanediol di(meth)acrylates, diethylene glycol di(meth)acrylates, triethylene glycol di(meth)acrylates, tetra ethylene glycol di(meth)acrylates, and polyethylene glycol di(meth)acrylates.
- the ethylenically unsaturated monomers that may be employed are alkoxylated and include ethoxylated and propoxylated (meth)acrylates.
- the polyfunctional ethylenically unsaturated monomer(s) of the crosslinking agent are crosslinked upon exposure heat or actinic radiation such as UV irradiation, whereupon the crosslinked polyfunctional ethylenically unsaturated monomer(s) acts like a mesh that holds at least a portion of the PVP in place (such a system is known as a semi-interpenetrating polymer network).
- a preferred weight ratio of total polyvinylpyrrolidone to polyfunctional ethylenically unsaturated monomer(s) is in the range of from about 0.5:1 to about 4:1, more preferably 1:1 to 2:1.
- Monofunctional ethylenically unsaturated monomers may also be optionally included in some compositions (and thus excluded in other compositions). Examples include mono(meth)acrylate esters, mono-vinyl compounds, and so forth.
- An additional hydrophilic polymer may also be optionally included in some compositions (and thus excluded in other compositions).
- examples of such polymers, which may be included (or excluded) include polyethylene glycol, polypropylene glycol, polyvinylpryrrolidone, hydrophilic urethane polymers, including acrylated urethanes, and so forth.
- a free radical initiator may also be optionally included in some compositions of the present disclosure (and thus excluded in other compositions).
- the free radical initiator may be, for example, a photoinitiator.
- free radical photoinitiators include benzophenones, ketones, acrylated amine synergists, alpha-amino ketones, acyl phosphine oxides including bis-acyl phosphine oxides, and benzil ketals.
- photoinitiators suitable for use herein include, but are not limited to, 2-phenyl-1-indanone; IRGACURE 184 from Ciba Specialty Chemicals, BENACURE 184 from Mayzo and SARCURE SR1122 from Sartomer, all of which are 1-hydroxylcyclohexylphenyl ketone (HCPK) initiators; BENACURE BP benzophenone; BENACURE 651 and IRGACURE 651, both of which are benzil dimethyl ketal or 2,2′dimethoxy-2-phenylacetophenone; BENACURE 1732 hydroxy-2-methyl-l-phenyl-1-propanone; IRGACURE 819 bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, IRGACURE 907 2-Methyl-1[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone; IRGACURE 369 morpholinoketone
- Photoinitiators are also available commercially in a variety of blends.
- Examples of commercially available blends include, but are not limited to, SARCURE SR1136 is a blend of 4-methylbenzophenone and benzophenone; SARCURE SR1137 is a blend of trimethylbenzophenone and methylbenzophenone; and BENACURE 500, a blend of 1-hydroxylcyclohexylphenyl ketone and benzophenone.
- additives may be employed in the coating compositions of the present disclosure including, but not limited to, flow or viscosity modifiers, antioxidants, coupling agents, surfactants, therapeutic agents, and so forth. Any such additives are typically incorporated into the composition at levels of 10% or less (e.g., ranging from 10% to 5% to 2% to 1% to 0.5% or less), based on the dry weight (i.e. excluding solvent) of the composition.
- the higher and lower molecular weight polyvinylpyrrolidones are suitably mixed with polyfunctional unsaturated crosslinking agent in a solvent that contains one or more solvent species.
- suitable solvents species include, but are not limited to, water and organic solvents including lower alcohols such as methanol, ethanol, and isopropyl alcohol (IPA), linear or cyclic carboxamides such as N,N-dimethylacetamide (DMAC), N,N-diethylacetamide, dimethylformamide (DMF), ethyl formamide, diethylformamide, N-methyl-2-pyrrolidone (NMP); dimethyl sulfoxide (DMSO), acetonitrile, acetone and acetyl acetone, acrylonitrile, benzonitriledimethyl acetamide, 1,4-dioxane, dipropyl sulfone, aromatic solvents such as toluene and
- Preferred solvent species are water soluble. Blends of solvent species such as those set forth above may be used.
- isopropyl alcohol in combination with water acts as a suitable solvent.
- the ratio of water to alcohol ranges from 0:100 to 50:50, more typically 10:90 to 50:50.
- liquid coating compositions for use in the present disclosure will contain from 1% to 5% solids, more typically from 2 to 4% solids.
- the mixture of solvent and coating composition may be applied to the medical device by any method known in the art including, but not limited to, spraying, dipping, rolling, painting (e.g., brush painting, sponge painting, etc.), and so forth.
- the coating may then be allowed to dry, by evaporation of the solvent.
- the solvent may be more readily evaporated at an elevated temperature, although room temperature drying is typically acceptable.
- substrate materials may be used in conjunction with the present disclosure including organic and inorganic substrates, typically polymer substrates, metal substrates and glass substrates, among others.
- metal substrates include pure metals such as platinum, gold, iridium and titanium, or and metal alloys such as stainless steel including platinum enriched stainless steel (PERSS), Nitinol alloys, and cobalt chromium alloys.
- PERSS platinum enriched stainless steel
- Nitinol alloys Nitinol alloys
- cobalt chromium alloys cobalt chromium alloys.
- polymer substrates include the following, among many others: (a) olefin homopolymers and copolymers, including homopolymers and copolymers of C2-C8 alkenes, for example, polyethylene and polypropylene, ethylene -vinyl acetate copolymers (EVA), and isobutylene-styrene copolymers, including block copolymers comprising one or more polystyrene blocks and one or more polyisobutylene blocks, for instance, poly(styrene-b-isobutylene-b-styrene) (SIBS), among others, (b) polyamides such as nylons , polyether-polyamide block copolymers such as poly(tetramethylene oxide-b-polyamide-12) block copolymer, available from Elf Atochem as PEBAX, among others, (c) fluoropolymers, including homopolymers and copolymers of C2-C8 alkenes in
- substrates include medical article substrates, specific example of which include medical device substrates, for instance, implantable or insertable medical device substrates.
- devices may thus be partially or completely coated with compositions in accordance with the present disclosure, including, for example, catheters (e.g., renal or vascular catheters), balloons, catheter shafts, guide wires, filters (e.g., vena cava filters), stents (including coronary vascular stents, cerebral stents, urethral stents, ureteral stents, biliary stents, tracheal stents, gastrointestinal stents and esophageal stents), stent grafts, cerebral aneurysm filler coils (including Guglilmi detachable coils and metal coils), vascular grafts, myocardial plugs, patches, pacemakers and pacemaker leads, heart valves, vascular valves, tissue engineering scaffolds for cartilage, bone, skin and
- the substrate may be treated with plasma or corona discharge before application of the coating composition.
- Coating compositions in accordance with the present disclosure may be cured, for example, by exposing the coating composition to heat or actinic radiation such as UV light for a short period of time. This initiates polymerization/crosslinking of the ethylenically unsaturated monomer(s).
- the polyfunctionality of at least some of the ethylenically unsaturated monomer(s) produces a high degree of crosslinking upon polymerization.
- At least for compositions based on acrylate esters it is generally desirable to cure in a low oxygen atmosphere, such as under a blanket of nitrogen, helium or argon gas.
- the amount of time needed to cure the surface is dependent on the source of energy, the relative amounts of constituents in the composition, the thickness of the coating desired, and other factors.
- the amount of time required for thermal cure is from about 1 to 30 minutes. UV curing requires less time and can generally be in the range of about two minutes or less. Curing around and along the substrate can be accomplished by incrementally or continuously using irradiation from multiple angles using spaced lamps and/or reflectors; rotation of the substrate, light source a light beam; longitudinal movement of the substrate, light source or light beam; or a combination of such techniques.
- the polymerizable composition is typically cured by irradiation with a suitable source of activating radiation such as ultraviolet (UV) radiation.
- a suitable source of activating radiation such as ultraviolet (UV) radiation.
- Light sources may be narrow or broad spectrum or laser beam sources.
- the composition is cured using a high intensity broad spectrum ultraviolet lamp such as mercury arc capillary lamps which have some output in the UVC region (280 nm-100 nm).
- a high intensity broad spectrum ultraviolet lamp such as mercury arc capillary lamps which have some output in the UVC region (280 nm-100 nm).
- the composition is photocured with UV lamps that are sequenced or pulsed in a way that allows for some heat dissipation during the curing cycle.
- the crosslinked coating thickness on the substrate is desirably in the range of from 0.1 micrometers or less to 20 micrometers or more (e.g., from 0.1 to 0.2 to 0.5 to 1 to 2 to 5 to 10 to 20 micrometers), more preferably, 0.1 to 5 micrometers.
- the coating thickness will be affected by the percent solids in the coating and the technique of application, among other factors. Multiple coatings may be applied to achieve a desired coating thickness.
- the coating compositions described herein may comprise a therapeutic agent, for example, selected from antimicrobial agents, antibiotic agents, anti-cancer agents, agents for treating calcifications, antirestenotic agents and antithrombotic agents, and combinations thereof, among others.
- the therapeutic agent(s) may be added to the coating composition prior to curing or applied onto the coating after it has been cured.
- Therapeutic agent(s) carried in the polymer coating may remain in the coating or elute out of the coating when the coating is wet, thereby delivering the therapeutic agent(s) to immediately adjacent areas of the body.
- PVP K90 weight average molecular weight 900,000, International Specialty Products, Wayne, N.J. USA.
- PVP K30 weight average molecular weight 58,000, International Specialty Products PVP K15, weight average molecular weight 10,000, International Specialty Products Neopentyl glycol diacrylate (NPGDA), Sigma-Aldrich, St. Louis, Mo., USA
- RO Reverse osmosis
- a solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA.
- PVP i.e., K90 100%, K90:K30 50:50 weight ratio, or K90:K15 50:50 weight ratio
- NPGDA were then added at a 4:1 PVP:NPGDA weight ratio to the solvent mixture to a total solids content of 5.5%.
- Catheters were coated along the outer shaft up to the balloon using a sponge wipe coater with the respective coating compositions.
- Coated catheters were mounted in spaced straight parallel arrangement in fixtures that were then placed in a UV curing chamber and subjected to a curing protocol that applied UV energy to the surface of the rotating catheters so that the coating was cured around the circumference of the tubing.
- Catheters were selected for lubricity and durability (L&D) testing.
- the coating thickness was determined on a central portion of the catheters. Average coating thicknesses for the coatings were in the range of about 0.5 to 1.5 micrometers.
- Example 2 Procedures analogous to that of Example 1 were followed with coating compositions of differing ratios of higher MW PVP to lower MW PVP.
- a solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA.
- PVP (100% K90, K90:K30 90:10 weight ratio, K90:K30 80:20 weight ratio, or K90:K30 70:30 weight ratio) and NPGDA were then added at a 2:1 PVP:NPGDA weight ratio to the solvent mixture to a total solids content of 3.3%.
- the catheters were inserted into a tubular test apparatus with bends constructed to simulate features of clinical deployment. Water was circulated over the catheters for a fixed period of time. Particles larger than 10 micrometers that were transferred into the circulating water were counted using a laser particle counter.
- solutions collected post laser count were filtered by using a Sum pore size filter, and the filter was subsequently analyzed by image analysis to obtain a particle size distribution.
- lower MW PVP i.e., K30
- K90 higher MW PVP
- the higher MW PVP appears to be able to contribute to insoluble particles
- the lower MW MVP i.e., K30
- particulates can be significant reduced by replacing a portion of the higher MW PVP (i.e., K90) with lower MW MVP (i.e., K30).
- Example 2 Procedures analogous to that of Example 1 were followed with coating compositions of differing solids content.
- a solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA.
- PVP (100% K90 or K90:K30 70:30 weight ratio) and NPGDA were then added at a 2:1 PVP:NPGDA weight ratio to the solvent mixture in varying total solids contents (2%, 3%, 3.3%, 4% or 5%).
- Example 2 Procedures analogous to that of Example 2 were followed with coating compositions of differing solids content.
- a solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA.
- PVP (100% K90 or K90:K30 70:30 weight ratio) and NPGDA were then added at a 2:1 PVP:NPGDA weight ratio to the solvent mixture at varying total solids contents (2%, 3%, 3.3%, 4% or 5%).
- Example 2 Procedures analogous to that of Example 1 were followed with coating compositions of differing ratios of PVP to NPGDA.
- a solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA.
- PVP (K90:K30 70:30 weight ratio) and NPGDA were then added to the solvent mixture at varying PVP:NPGDA weight ratios (2:1 to 1:1) to a total solids content of 3.3%.
- Example 2 Procedures analogous to that of Example 2 were followed with coating compositions of differing ratios of PVP to NPGDA.
- a solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA.
- PVP (100% K90 or K90:K30 70:30 weight ratio) and NPGDA were then added to the solvent mixture at varying PVP:NPGDA weight ratios (2:1 to 1:1) to a total solids content of 3.3%.
- the PVP:NPGDA weight ratio for 100% K90 was 2:1.
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Abstract
In one aspect, the present disclosure pertains to lubricous coating compositions that comprise (a) a higher molecular weight polyvinylpyrrolidone, (b) a lower molecular weight polyvinylpyrrolidone, and (c) a polyfunctional unsaturated crosslinking agent. In some embodiments, such lubricous coating compositions are present in crosslinked form on the surface of a medical article. In some embodiments, the lubricous coating compositions further comprise a solvent, in which case such compositions may be, for example, applied to a substrate in the form of a layer and subsequently crosslinked, thereby forming a lubricious coating on the substrate. In another aspect, the present disclosure is directed to methods for forming various medical articles.
Description
- This application claims priority under 35 USC §119(e) to U.S. Provisional Application Ser. No. 61/846,376, filed on Jul. 15, 2013, the entire contents of which are hereby incorporated by reference.
- There is a desire in the medical arts to provide a variety of medical articles with increased lubricity relative to the materials commonly employed in their manufacture. This is particularly desirable, for instance, when the medical articles are medical devices to be implanted or inserted into the body. For example, as minimally invasive surgical techniques have improved, it has become increasingly common to insert and retrieve medical devices through catheters and the like having considerable length. Accordingly, it is desirable to minimize friction between the catheters that carry such devices and the devices themselves as well as with tissue with which they may come in contact. In the past, the industry has employed various hydrophobic oils and coatings such as olive oil, silicone, and the like as lubricants. Hydrophilic coatings, particularly hydrogels, also have been employed to impart lubricity to a variety of medical devices.
- In one aspect, the present invention pertains to lubricous coating compositions that comprise (a) a higher molecular weight polyvinylpyrrolidone (also referred to herein as higher MW PVP), (b) a lower molecular weight polyvinylpyrrolidone (also referred to herein as lower MW PVP), and (c) a polyfunctional unsaturated crosslinking agent.
- In some embodiments, such lubricous coating compositions are present in crosslinked form on the surface of a medical article.
- In some embodiments, the lubricous coating compositions further comprise a solvent. Such compositions may be, for example, applied to a substrate in the form of a layer and subsequently crosslinked, thereby forming a lubricious coating on the substrate.
- In another aspect, the present invention is directed to methods for forming various medical articles.
- An advantage of the present invention is that coatings can be provided which are both lubricious and durable. Another advantage of the present invention is that coatings can be provided which produce very low levels of particulates when in contact with aqueous fluids.
- These and other aspects, embodiments and advantages of the present invention will become immediately apparent to those of ordinary skill in the art upon review of the Detailed Description and claims to follow.
-
FIG. 1 is a plot of frictional force (g) vs. number of friction cycles for different grades of PVP. -
FIG. 2 is a plot of frictional force (g) vs. number of friction cycles for different ratios of higher MW PVP to lower MW PVP. -
FIG. 3 is a plot of relative particle count (>10 micrometer) as a function of different ratios of higher MW PVP to lower MW PVP. -
FIG. 4 is a plot of relative particle count (>50 micrometer) as a function of different ratios of higher MW PVP to lower MW PVP. -
FIG. 5 is a plot of frictional force (g) vs. number of friction cycles for different overall solids content. -
FIG. 6 is a plot of relative particle count (>10 micrometer) as a function of overall solids content. -
FIG. 7 is a plot of relative particle count (>50 micrometer) as a function of overall solids content. -
FIG. 8 is a plot of frictional force (g) vs. number of friction cycles for different ratios of PVP to NPGDA. -
FIG. 9 is a plot of relative particle count (>50 micrometer) as a function of different ratios of PVP to NPGDA. - A more complete understanding of the present invention is available by reference to the following detailed description of numerous aspects and embodiments of the invention. The detailed description of the invention which follows is intended to illustrate but not limit the invention.
- In one aspect, the present disclosure pertains to lubricous coating compositions for various articles. The compositions comprise a mixture of a higher molecular weight polyvinylpyrrolidone (higher MW PVP) and a lower molecular weight polyvinylpyrrolidone (lower MW PVP) as well as a crosslinking agent.
- Because it is difficult to measure molecular weight of a sample of PVP directly, the K-value has been adopted to classify the molecular weight of PVP. The K-value is a function of the average degree of polymerization and intrinsic viscosity of a given polymer and is calculated from the kinematic viscosity of a 1% w/v aqueous solution of the polymer.
- As used herein, a higher MW PVP is defined as one having a K-value between 60 and 95 (e.g., ranging from 60 to 65 to 70 to 75 to 80 to 85 to 90 to 95). This corresponds to a weight average molecular weight between approximately 100,000 and 1,300,000. In preferred embodiments, the higher MW PVP will have a K-value between 85 and 95.
- As used herein, a lower MW PVP is defined as one having a K-value between 5 and 35 (e.g., ranging from 5 to 10 to 15 to 20 to 25 to 30 to 35). This corresponds to a weight average molecular weight between approximately 2,000 and 95,000. In preferred embodiments, the lower MW PVP will have a K-value between 15 and 32.
- Examples of polyvinylpyrrolidone materials useful in the present disclosure include Povidone K12, Povidone K15, Povidone K17, Povidone K25, Povidone K30, Povidone K60, Povidone K90 and Povidone K120, among others. Polyvinylpyrrolidone is available from BASF Corp, Parsippany, N.J., USA under the tradenames Kollidon® and Luvitec® and from Ashland Inc., Halethorpe, Md., USA as Plasdone®.
- Depending on the composition, the crosslinking agent may be substantially uncrosslinked (degree of crosslinking less than 5%), partially crosslinked (degree of crosslinking between 5% and 95%), or substantially completely crosslinked (degree of crosslinking greater than 99%. The degree of crosslinking may range from 1% or less to 2% to 5% to 10% to 25% to 50% to 75% to 90% to 95% to 98% to 99% or more.
- In some embodiments, the lubricous coating compositions are present on the surface of a medical article in solid form, with the crosslinking agent being at least partially crosslinked.
- In some embodiments, the lubricous coating compositions are present in liquid form, with the crosslinking agent being substantially uncrosslinked. Such compositions may be, for example, applied to a substrate in the form of a layer and then at least partially crosslinked, thereby forming a lubricious coating on the substrate. In some embodiments, such compositions comprise a solvent, which may be removed before, during and/or after a crosslinking step.
- Polyfunctional ethylenically unsaturated monomers are preferred as crosslinking agents. The polyfunctional ethylenically unsaturated monomers are compounds, including monomeric and oligomeric compounds, that have a two or more ethylenically unsaturated groups thereon that may be readily polymerized by a radical mechanism to form a polymer. Typically, such compounds have a number average of about 5000 or less, more typically about 1000 or less. Suitable polyfunctional ethylenically unsaturated monomers include di- and tri-functional acrylate and methacrylate compounds, collectively referred to as (meth)acrylate compounds, including (meth)acrylate esters, as well as divinyl and trivinyl compounds. Specific examples of polyfunctional ethylenically unsaturated monomers that may be used in the compositions of the present disclosure include neopentyl glycol di(meth)acrylates, including neopentyl glycol diacrylate (NPGDA), ethylene glycol di(meth)acrylates, 1,3-propylene glycol di(meth)acrylates, 1,4-butanediol di(meth)acrylates, 1,6-hexanediol di(meth)acrylates, diethylene glycol di(meth)acrylates, triethylene glycol di(meth)acrylates, tetra ethylene glycol di(meth)acrylates, and polyethylene glycol di(meth)acrylates. In some embodiments the ethylenically unsaturated monomers that may be employed are alkoxylated and include ethoxylated and propoxylated (meth)acrylates.
- Without being bound by theory, it is believed that the polyfunctional ethylenically unsaturated monomer(s) of the crosslinking agent are crosslinked upon exposure heat or actinic radiation such as UV irradiation, whereupon the crosslinked polyfunctional ethylenically unsaturated monomer(s) acts like a mesh that holds at least a portion of the PVP in place (such a system is known as a semi-interpenetrating polymer network).
- In some embodiments, a preferred weight ratio of total polyvinylpyrrolidone to polyfunctional ethylenically unsaturated monomer(s) is in the range of from about 0.5:1 to about 4:1, more preferably 1:1 to 2:1.
- Monofunctional ethylenically unsaturated monomers may also be optionally included in some compositions (and thus excluded in other compositions). Examples include mono(meth)acrylate esters, mono-vinyl compounds, and so forth.
- An additional hydrophilic polymer may also be optionally included in some compositions (and thus excluded in other compositions). Examples of such polymers, which may be included (or excluded), include polyethylene glycol, polypropylene glycol, polyvinylpryrrolidone, hydrophilic urethane polymers, including acrylated urethanes, and so forth.
- A free radical initiator may also be optionally included in some compositions of the present disclosure (and thus excluded in other compositions). The free radical initiator may be, for example, a photoinitiator. Non-limiting examples of free radical photoinitiators that may be employed include benzophenones, ketones, acrylated amine synergists, alpha-amino ketones, acyl phosphine oxides including bis-acyl phosphine oxides, and benzil ketals. More specific examples of photoinitiators suitable for use herein include, but are not limited to, 2-phenyl-1-indanone; IRGACURE 184 from Ciba Specialty Chemicals, BENACURE 184 from Mayzo and SARCURE SR1122 from Sartomer, all of which are 1-hydroxylcyclohexylphenyl ketone (HCPK) initiators; BENACURE BP benzophenone; BENACURE 651 and IRGACURE 651, both of which are benzil dimethyl ketal or 2,2′dimethoxy-2-phenylacetophenone; BENACURE 1732 hydroxy-2-methyl-l-phenyl-1-propanone; IRGACURE 819 bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, IRGACURE 907 2-Methyl-1[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone; IRGACURE 369 morpholinoketone; and so forth and blends thereof. Photoinitiators are also available commercially in a variety of blends. Examples of commercially available blends include, but are not limited to, SARCURE SR1136 is a blend of 4-methylbenzophenone and benzophenone; SARCURE SR1137 is a blend of trimethylbenzophenone and methylbenzophenone; and BENACURE 500, a blend of 1-hydroxylcyclohexylphenyl ketone and benzophenone.
- Other optional additives may be employed in the coating compositions of the present disclosure including, but not limited to, flow or viscosity modifiers, antioxidants, coupling agents, surfactants, therapeutic agents, and so forth. Any such additives are typically incorporated into the composition at levels of 10% or less (e.g., ranging from 10% to 5% to 2% to 1% to 0.5% or less), based on the dry weight (i.e. excluding solvent) of the composition.
- In preparing liquid coating compositions for application to a substrate, the higher and lower molecular weight polyvinylpyrrolidones are suitably mixed with polyfunctional unsaturated crosslinking agent in a solvent that contains one or more solvent species. Examples of suitable solvents species include, but are not limited to, water and organic solvents including lower alcohols such as methanol, ethanol, and isopropyl alcohol (IPA), linear or cyclic carboxamides such as N,N-dimethylacetamide (DMAC), N,N-diethylacetamide, dimethylformamide (DMF), ethyl formamide, diethylformamide, N-methyl-2-pyrrolidone (NMP); dimethyl sulfoxide (DMSO), acetonitrile, acetone and acetyl acetone, acrylonitrile, benzonitriledimethyl acetamide, 1,4-dioxane, dipropyl sulfone, aromatic solvents such as toluene and xylene, nitrobenzene, phenylacetate, propionitrile, and so forth. Preferred solvent species are water soluble. Blends of solvent species such as those set forth above may be used. In one preferred embodiment, isopropyl alcohol in combination with water acts as a suitable solvent. In many embodiments, the ratio of water to alcohol ranges from 0:100 to 50:50, more typically 10:90 to 50:50.
- Typically, the liquid coating compositions for use in the present disclosure will contain from 1% to 5% solids, more typically from 2 to 4% solids.
- The mixture of solvent and coating composition may be applied to the medical device by any method known in the art including, but not limited to, spraying, dipping, rolling, painting (e.g., brush painting, sponge painting, etc.), and so forth. The coating may then be allowed to dry, by evaporation of the solvent. The solvent may be more readily evaporated at an elevated temperature, although room temperature drying is typically acceptable.
- A variety of substrate materials may be used in conjunction with the present disclosure including organic and inorganic substrates, typically polymer substrates, metal substrates and glass substrates, among others. Examples of metal substrates include pure metals such as platinum, gold, iridium and titanium, or and metal alloys such as stainless steel including platinum enriched stainless steel (PERSS), Nitinol alloys, and cobalt chromium alloys.
- Examples of polymer substrates include the following, among many others: (a) olefin homopolymers and copolymers, including homopolymers and copolymers of C2-C8 alkenes, for example, polyethylene and polypropylene, ethylene -vinyl acetate copolymers (EVA), and isobutylene-styrene copolymers, including block copolymers comprising one or more polystyrene blocks and one or more polyisobutylene blocks, for instance, poly(styrene-b-isobutylene-b-styrene) (SIBS), among others, (b) polyamides such as nylons , polyether-polyamide block copolymers such as poly(tetramethylene oxide-b-polyamide-12) block copolymer, available from Elf Atochem as PEBAX, among others, (c) fluoropolymers, including homopolymers and copolymers of C2-C8 alkenes in which one or more hydrogen atoms are substituted with fluorine, for example, polytetrafluoroethylene (PTFE), polyhexafluoropropene (PVDF), polyvinylidene fluoride (PVDF), and poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP), among others, (d) polyurethane copolymers, including copolymers that are polyether based, polyester based, polycarbonate based, aromatic based and aliphatic based, including polyisobutylene based polyurethanes (PIB-PU), among others, and (e) silicone homopolymers and copolymers (also referred to as polysiloxanes) such as polydimethylsiloxane.
- Examples of substrates include medical article substrates, specific example of which include medical device substrates, for instance, implantable or insertable medical device substrates. A variety of devices may thus be partially or completely coated with compositions in accordance with the present disclosure, including, for example, catheters (e.g., renal or vascular catheters), balloons, catheter shafts, guide wires, filters (e.g., vena cava filters), stents (including coronary vascular stents, cerebral stents, urethral stents, ureteral stents, biliary stents, tracheal stents, gastrointestinal stents and esophageal stents), stent grafts, cerebral aneurysm filler coils (including Guglilmi detachable coils and metal coils), vascular grafts, myocardial plugs, patches, pacemakers and pacemaker leads, heart valves, vascular valves, tissue engineering scaffolds for cartilage, bone, skin and other in vivo tissue regeneration, and so forth.
- Typically no primer layer or coupling agent is applied to the substrate before the coating is applied. However, in some embodiments, the substrate may be treated with plasma or corona discharge before application of the coating composition.
- Coating compositions in accordance with the present disclosure may be cured, for example, by exposing the coating composition to heat or actinic radiation such as UV light for a short period of time. This initiates polymerization/crosslinking of the ethylenically unsaturated monomer(s). The polyfunctionality of at least some of the ethylenically unsaturated monomer(s) produces a high degree of crosslinking upon polymerization. At least for compositions based on acrylate esters it is generally desirable to cure in a low oxygen atmosphere, such as under a blanket of nitrogen, helium or argon gas. The amount of time needed to cure the surface is dependent on the source of energy, the relative amounts of constituents in the composition, the thickness of the coating desired, and other factors. Generally, the amount of time required for thermal cure is from about 1 to 30 minutes. UV curing requires less time and can generally be in the range of about two minutes or less. Curing around and along the substrate can be accomplished by incrementally or continuously using irradiation from multiple angles using spaced lamps and/or reflectors; rotation of the substrate, light source a light beam; longitudinal movement of the substrate, light source or light beam; or a combination of such techniques. The polymerizable composition is typically cured by irradiation with a suitable source of activating radiation such as ultraviolet (UV) radiation. Light sources may be narrow or broad spectrum or laser beam sources. Suitably the composition is cured using a high intensity broad spectrum ultraviolet lamp such as mercury arc capillary lamps which have some output in the UVC region (280 nm-100 nm). In some embodiments the composition is photocured with UV lamps that are sequenced or pulsed in a way that allows for some heat dissipation during the curing cycle.
- In some embodiments the crosslinked coating thickness on the substrate is desirably in the range of from 0.1 micrometers or less to 20 micrometers or more (e.g., from 0.1 to 0.2 to 0.5 to 1 to 2 to 5 to 10 to 20 micrometers), more preferably, 0.1 to 5 micrometers. The coating thickness will be affected by the percent solids in the coating and the technique of application, among other factors. Multiple coatings may be applied to achieve a desired coating thickness.
- As noted above, in some embodiments the coating compositions described herein may comprise a therapeutic agent, for example, selected from antimicrobial agents, antibiotic agents, anti-cancer agents, agents for treating calcifications, antirestenotic agents and antithrombotic agents, and combinations thereof, among others. The therapeutic agent(s) may be added to the coating composition prior to curing or applied onto the coating after it has been cured. Therapeutic agent(s) carried in the polymer coating may remain in the coating or elute out of the coating when the coating is wet, thereby delivering the therapeutic agent(s) to immediately adjacent areas of the body.
- The invention is illustrated by the following non-limiting examples.
- Raw Materials:
- PVP K90, weight average molecular weight 900,000, International Specialty Products, Wayne, N.J. USA.
PVP K30, weight average molecular weight 58,000, International Specialty Products
PVP K15, weight average molecular weight 10,000, International Specialty Products
Neopentyl glycol diacrylate (NPGDA), Sigma-Aldrich, St. Louis, Mo., USA - Reverse osmosis (RO) water
- Over-the-wire catheters manufactured by Boston Scientific Corporation that had a distal shaft of Pebax™ 7033 were employed in these Examples. These catheters were exposed to a argon plasma in a commercial treatment system (March Plasma Systems, Concord, Calif., USA) prior to coating. The coatings were applied and cured within a short time of plasma treatment.
- A solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA. PVP (i.e.,
K90 100%, K90:K30 50:50 weight ratio, or K90:K15 50:50 weight ratio) and NPGDA were then added at a 4:1 PVP:NPGDA weight ratio to the solvent mixture to a total solids content of 5.5%. - Catheters were coated along the outer shaft up to the balloon using a sponge wipe coater with the respective coating compositions. Coated catheters were mounted in spaced straight parallel arrangement in fixtures that were then placed in a UV curing chamber and subjected to a curing protocol that applied UV energy to the surface of the rotating catheters so that the coating was cured around the circumference of the tubing.
- Catheters were selected for lubricity and durability (L&D) testing. A catheter was cut into equal length pieces, the pieces submerged in water, weighed down with a given weight and subjected to reciprocal pulling and pushing cycles, measuring the frictional force (in grams) required to move the catheter piece initially (t=0) and through successive cycles. The coating thickness was determined on a central portion of the catheters. Average coating thicknesses for the coatings were in the range of about 0.5 to 1.5 micrometers.
- As seen from
FIG. 1 , the addition of lower MW PVP to the higher MW PVP in a 50:50 weight ratio improved lubricity, but resulted in less durability of the lubricity. - Procedures analogous to that of Example 1 were followed with coating compositions of differing weight ratios of higher MW PVP to lower MW PVP. A solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA. PVP (100% K90, K90:K30 99:1 weight ratio, K90:K30 95:5 weight ratio, K90:K30 90:10 weight ratio, K90:K30 80:20 weight ratio or K90:K30 70:30 weight ratio) and NPGDA were then added at a 2:1 PVP:NPGDA weight ratio to the solvent mixture to a total solids content of 3.3%.
- As can be seen from
FIG. 2 , lubricity and durability are acceptable over the entire range of higher MW PVP:lower MW PVP ratios, although the K90:K30 80:20 formulation exhibited slightly lower lubricity. - Procedures analogous to that of Example 1 were followed with coating compositions of differing ratios of higher MW PVP to lower MW PVP. A solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA. PVP (100% K90, K90:K30 90:10 weight ratio, K90:K30 80:20 weight ratio, or K90:K30 70:30 weight ratio) and NPGDA were then added at a 2:1 PVP:NPGDA weight ratio to the solvent mixture to a total solids content of 3.3%.
- For small particles, catheters were used for measurement of surface particulate count at t=0. The catheters were inserted into a tubular test apparatus with bends constructed to simulate features of clinical deployment. Water was circulated over the catheters for a fixed period of time. Particles larger than 10 micrometers that were transferred into the circulating water were counted using a laser particle counter. For large particles (>50 micron), solutions collected post laser count were filtered by using a Sum pore size filter, and the filter was subsequently analyzed by image analysis to obtain a particle size distribution.
- As can be seen from
FIGS. 3 and 4 , small particle size counts were somewhat improved, and large particle counts were dramatically improved by the addition of lower MW PVP to the coating at all ratios. - Without wishing to be bound by theory, it is noted that lower MW PVP (i.e., K30) has been shown to be nearly 100% soluble (i.e., about 99%) when cured. The solubility of higher MW PVP (i.e., K90), on the other hand, has been shown to be much less soluble (i.e., about 33.5%) upon cure. Thus the higher MW PVP (i.e., K90) appears to be able to contribute to insoluble particles whereas the lower MW MVP (i.e., K30) cannot. Consequently, particulates can be significant reduced by replacing a portion of the higher MW PVP (i.e., K90) with lower MW MVP (i.e., K30).
- Procedures analogous to that of Example 1 were followed with coating compositions of differing solids content. A solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA. PVP (100% K90 or K90:K30 70:30 weight ratio) and NPGDA were then added at a 2:1 PVP:NPGDA weight ratio to the solvent mixture in varying total solids contents (2%, 3%, 3.3%, 4% or 5%).
- As seen from FIG. 5, good overall lubricity and durability performance was obtained for solids content ranging from 3% to 4%. The high solids content (5.5%) composition was found to lose durability after several passes. The low solids content (2%) composition was found to exhibit lower lubricity, possibly due to insufficient coating material.
- Procedures analogous to that of Example 2 were followed with coating compositions of differing solids content. A solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA. PVP (100% K90 or K90:K30 70:30 weight ratio) and NPGDA were then added at a 2:1 PVP:NPGDA weight ratio to the solvent mixture at varying total solids contents (2%, 3%, 3.3%, 4% or 5%).
- As can be seen from
FIGS. 6 and 7 , no significant particle size trends were observed between 2% to 5.5% solid. Also, small particle size counts were significantly improved and large particle counts were dramatically improved by the addition of lower MW PVP to the coating. - Procedures analogous to that of Example 1 were followed with coating compositions of differing ratios of PVP to NPGDA. A solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA. PVP (K90:K30 70:30 weight ratio) and NPGDA were then added to the solvent mixture at varying PVP:NPGDA weight ratios (2:1 to 1:1) to a total solids content of 3.3%.
- As seen from
FIG. 8 , good overall lubricity and durability performance was obtained for PVP:NPGDA weight ratios ranging from 2:1 to 1:1. - Procedures analogous to that of Example 2 were followed with coating compositions of differing ratios of PVP to NPGDA. A solvent mixture of water and IPA was prepared at 1 to 4 weight basis water to IPA. PVP (100% K90 or K90:K30 70:30 weight ratio) and NPGDA were then added to the solvent mixture at varying PVP:NPGDA weight ratios (2:1 to 1:1) to a total solids content of 3.3%. The PVP:NPGDA weight ratio for 100% K90 was 2:1.
- As seen from FIG. 9, no significant particle size trend was observed for K90:K30 mixtures (70:30 weight ratio) with PVP:NPGDA weight ratios ranging from 2:1 to 1:1. Large particle size counts were significantly improved by the addition of lower MW PVP to the coating.
- Although various embodiments are specifically illustrated and described herein, it will be appreciated that modifications and variations of the present disclosure are covered by the above teachings and are within the purview of the appended claims without departing from the spirit and intended scope of the invention.
Claims (19)
1. A lubricous coating composition comprising (a) a higher molecular weight polyvinylpyrrolidone, (b) a lower molecular weight polyvinylpyrrolidone, and (c) a polyfunctional unsaturated crosslinking agent.
2. The lubricous coating composition of claim 1 , wherein the higher molecular weight polyvinylpyrrolidone has a K-value ranging from 85 to 95 and wherein the lower molecular weight polyvinylpyrrolidone has a K-value ranging from 15 to 32.
3. The lubricous coating composition of claim 1 , wherein the weight ratio of higher molecular weight polyvinylpyrrolidone to lower molecular weight polyvinylpyrrolidone ranges from 70:30 to 90:10.
4. The lubricous coating composition of claim 1 , wherein the crosslinking agent is a polyfunctional ethylenically unsaturated monomer selected from a polyfunctional acrylate compound, polyfunctional methacrylate compound and a polyfunctional vinyl compound.
5. The lubricous coating composition of claim 4 , wherein the crosslinking agent is neopentyl glycol diacrylate.
6. The lubricous coating composition of claim 5 , wherein the weight ratio of total polyvinylpyrrolidone to neopentyl glycol diacrylate ranges from 0.5:1 to 4:1.
7. The lubricous coating composition of claim 1 , further comprising a solvent.
8. The lubricous coating composition of claim 7 , wherein the solvent comprises a lower alcohol and water.
9. The lubricous coating composition of claim 8 , wherein the lower alcohol is isopropanol.
10. The lubricous coating composition of claim 9 , wherein the weight ratio of water to isopropanol ranges from 50:50 to 10:90.
11. The lubricous coating composition of claim 9 , wherein the total solids ranges from 2.5 wt % to 5.5 wt %.
12. The lubricous coating composition of claim 1 , further comprising a therapeutic agent.
13. The lubricous coating composition of claim 12 , wherein the therapeutic agent is selected from antimicrobial agents, antibiotic agents, anti-cancer agents, agents for treating calcifications, antirestenotic agents, antithrombotic agents and combinations thereof
14. A medical article comprising a medical article substrate that is at least partially covered by a layer of the lubricous coating composition in accordance with claim 1 , wherein the polyfunctional unsaturated crosslinking agent is at least partially crosslinked.
15. The medical article of claim 14 , wherein the layer ranges from 0.1 to 20 micrometers in thickness.
16. The medical article of claim 14 , wherein the medical article is an implantable or insertable medical device.
17. A method comprising applying the lubricous coating composition of claim 8 to a substrate in the form of a layer, removing at least a portion of the solvent, and crosslinking the composition by applying of UV light.
18. An article made by the method of claim 17 , wherein the article is a medical article comprising a lubricious coating.
19. The article of claim 18 , wherein the medical article is an implantable or insertable medical device.
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US14/330,734 US20150018431A1 (en) | 2013-07-15 | 2014-07-14 | Lubricious Coating Compositions |
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EP3021882A1 (en) | 2016-05-25 |
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