WO1989011500A1 - Materiaux polymeres multicouches non gonflants hydrophiles et leur procede de fabrication - Google Patents

Materiaux polymeres multicouches non gonflants hydrophiles et leur procede de fabrication Download PDF

Info

Publication number
WO1989011500A1
WO1989011500A1 PCT/AU1989/000220 AU8900220W WO8911500A1 WO 1989011500 A1 WO1989011500 A1 WO 1989011500A1 AU 8900220 W AU8900220 W AU 8900220W WO 8911500 A1 WO8911500 A1 WO 8911500A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymeric material
layer
vapour
bulk
surface layer
Prior art date
Application number
PCT/AU1989/000220
Other languages
English (en)
Inventor
Hans Jorg Griesser
John Gerard Steele
Graham Johnson
Jonathon Howard Hodgkin
Original Assignee
Commonwealth Scientific And Industrial Research Or
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Commonwealth Scientific And Industrial Research Or filed Critical Commonwealth Scientific And Industrial Research Or
Publication of WO1989011500A1 publication Critical patent/WO1989011500A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • 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
    • 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
    • A61L27/36—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix
    • 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
    • A61L27/60—Materials for use in artificial skin
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N5/00—Undifferentiated human, animal or plant cells, e.g. cell lines; Tissues; Cultivation or maintenance thereof; Culture media therefor
    • C12N5/0068—General culture methods using substrates
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N2533/00—Supports or coatings for cell culture, characterised by material
    • C12N2533/30—Synthetic polymers

Definitions

  • the present invention relates to hydrophillic non-swelling multilayer polymeric materials and a process for producing such materials.
  • Corona Discharge, Flame Treatment, Acid Etching, and a number of other methods intended to perform chemical modification of the surface are Corona Discharge, Flame Treatment, Acid Etching, and a number of other methods intended to perform chemical modification of the surface. Disadvantages of these techniques comprise the use of or production of hazardous chemicals, the often excessive depth of treatment, non-uniformity of treatment at a microscopic level, and often severe etching and pitting that leads to changes in surface topography. The depth of treatment is important because with thin, plastic webs the bulk properties soon become affected to an excessive extent.
  • a glow discharge in air or oxygen has been used to render polymeric surfaces more hydrophilic. The treatment leads to formation of polar, oxygen containing functionalities on the surface.
  • the main disadvantage of this approach is that the treatment is not permanent due to reorientation of the polymer chains with time as a result of unavoidable, thermally driven chain segmental motions. Wettability by water decreases as the hydrophilic surface groups produced by treatment become buried inside the polymer, as described by H. Yasuda et al. in J. Polym. Sci.: Polym. Phys. Ed., 19., 1285 (1981). A glow discharge in an atmosphere comprising water vapour as an essential component, and optionally organic compounds, has also been used (Japan 59-15569). Improved hydrophilicity of the treated surface was obtained: it was, however, not demonstrated that the treated surface was immune to slow reorientation and burial of the created groups.
  • a multilayer polymeric material including a first layer formed from a bulk polymeric material; and at least a second layer deposited by plasma polymerisation on at least a surface of the first polymeric layer to increase the hydrophilic nature of said surface.
  • the multilayer polymeric material may take the form of a biomedical implant. It will be understood that by provision of the multilayer structure the invention achieves improvement of bulk and surface properties independently.
  • the bulk polymeric material which forms the first layer may be selected to provide suitable mechanical properties depending on the particular application to which the material is to be put while the second layer may be selected for its surface chemical properties.
  • any one of the known polymeric materials may be used for the bulk polymeric material because the process of this invention can proceed without regard for the composition of the bulk polymeric material and in all cases substantially improved wettability of the treated surfaces is obtained.
  • Particularly preferred polymers include perfluorinated polymers including polytetrafluoroethylene, polyethylene, polyesters, polyurethanes, copolymers thereof and mixtures thereof.
  • the invention is particularly applicable to the normally unreactive perfluorinated polymeric materials such as polytetrafluoroethylene or fluorinated ethylene propylene polymers (FEP, Du Pont) .
  • the second surface layer may be formed from any suitable material amenable to plasma polymerisation techniques that will increase the hydrophilic nature of the multilayer composite. It is preferred that the second surface layer is a relatively thin layer. We have found that such a surface layer may be formed via plasma polymerisation. It has been found advantageously that the second surface layer bonds to the first polymeric layer with substantially no penetration thereinto. As explained above it has been found that significant penetration may affect the desirable bulk properties of the first polymeric layer.
  • the second surface layer may be formed from a plasma in a vapour composition including at least one organic monomeric material capable of polymerisation under plasma polymerisation conditions.
  • the organic monomeric material may include at least one compound selected from saturated alcohols, amines, and the like, derivatives thereof and precursors therefor.
  • the vapour composition utilised to form the second surface layer may further include at least one inorganic gas.
  • vapour composition does not include significant amounts of water vapour.
  • the at least one organic monomeric material may include saturated alcohols and saturated amines including lower saturated alcohols and amines.
  • the lower saturated alcohols and amines may be selected from substituted or unsubstituted C 1,-Co 0 alcohols and amines.
  • the compounds methanol, ethanol, n-propanol, n-butanol, methylamine, ethylamine, n-propylamine, and n-butylamine are preferred.
  • the lower saturated alcohols and amines may include one or more substituents selected from halogens, amino groups and the like.
  • the inorganic gas may be of any suitable type. Oxygen, hydrogen, nitrogen (N 2 ) and the noble gases Helium, Nitrogen, Argon and Neon and the like may be used.
  • the vapour composition may include one or more additional components. Additional components may include additional monomeric material and/or other components selected to improve the properties of the layer formed.
  • the second surface layer of the multilayer polymeric material may be contacted with a serum component.
  • the serum component may include an adhesive protein for example an adhesive glycoprotein.
  • the serum component may provide a serum adhesive protein e.g. a glycoprotein which becomes adsorbed onto the surface, and participate in HUAE cell attachment and spreading onto the surface.
  • Preferred serum components include fibronectin (Fn), vitronectin (Vn) , (see Grinnell (1976, Exp. Cell Res., 97, 265-274; Underwood and Bennett, 1989, J. Cell Sci., in press) and thrombospondin or adhesive gragments thereof.
  • the adhesive proteins are adsorbed by the hydrophilic surface layer to form a polymer-protein complex. Such complex assists in the attachment and subsequent growth of animal cells.
  • the multilayer polymeric material may take the form of a biomedical implant. Accordingly, in a further aspect of the present invention there is provided a biomedical implant including a polymeric article formed from a bulk polymeric material; said polymeric article bearing a surface layer deposited on at least a surface thereof by plasma polymerisation to increase the hydrophilic nature of the surface.
  • the bulk polymeric material is selected from perfluorinated polymers, polyethylene, polyesters, polyurethanes, copolymers thereof and mixtures thereof.
  • the polymeric article may be formed into a desired final shape, dependent upon its application prior to plasma polymerisation treatment.
  • the first polymeric article may take the form of a biomedical implant.
  • the surface layer is formed from a vapour composition including at least one organic monomeric material capable of polymerisation under plasma polymeristaion conditions.
  • the surface layer of the biomedical implant is contacted with a serum component.
  • the serum component is selected from fibronectin, vitronectin, thrombospondin or adhesive fragments thereof.
  • a process for the preparation of a multilayer polymeric material which process includes providing a first polymeric material formed into a desired final shape from a bulk polymer; depositing from the vapour phase a second layer via a plasma polymerisation reaction in a vapour composition containing at least one monomeric material to form a surface layer on at least one surface of the first polymeric material; if desired depositing further layers of different ⁇ , composition by plasma polymerisation in vapours of composition different to that used to produce the second layer.
  • the vapour composition desirably includes no more than approximately 20% v/v water vapour more preferably no more than approximately 5% v/v water vapour.
  • the effect of water vapour is to reduce or prevent cross linking of the monomer which appears in the atmosphere, with the result that the vapour created may not be immune to slow reorientation and burial of the created groups and may not be resistant to swelling.
  • a plasma polymerisation (also known as glow discharge) may be produced by electrical discharge in a gas atmosphere at reduced pressure ("vacuum"). It creates a stable, partially ionized gas that may be utilized as a source of reactive species.
  • a wide variety of chemical compounds can be utilized for effecting reactions on the surface of the first polymer layer because the gas plasma environment activates even chemical compounds that are unreactive under normal conditions. Surface topography does not change measurably unless exposure to the plasma is performed for extended periods of time usually much exceeding the time required for achieving the desired formation of the second or subsequent layer. There occurs, therefore, much less alteration of the properties of the bulk polymer than with alternative technologies.
  • the process may further include providing a serum component including an adhesive protein; and contacting the second surface layer with the serum component.
  • the serum component is selected from fibronectin, vitronectin, thrombospondin or adhesive fragments thereof.
  • the serum component is provided in a cell culture medium.
  • the cell culture medium may for example consist of an equal mixture of McCoy 5A (modified) (CSL laboratories, Melbourne) and BM86-Wissler (Boehringer- Mannheim) media supplemented with 30% v/v foetal bovine serum (Cytosystems, Sydney), 40 ng/ml fibroblast growth factor (biomedical Technologies Inc.) 60 ug/ml endothellal cell growth supplement (Collaborative Research) , 20 ug/ml insulin (G1BCO), 60 ug/ml pencillin (Glaxo) and 100 ug/ml streptomycin (Glaxo) .
  • McCoy 5A modified
  • BM86-Wissler Boehringer- Mannheim
  • the biomedical implant according to the present invention may be utilized for the attachment and growth of animal cells in vitro. Accordingly, in a still further aspect of the present invention there is provided a source of animal cells; and a biomedical implant including a first polymeric article formed from a bulk polymer material; said first polymeric article bearing a surface layer deposited on at least a surface thereof by plasma polymerisation to increase the hydrophilic nature of the surface.
  • a source of animal cells and a biomedical implant including a first polymeric article formed from a bulk polymer material; said first polymeric article bearing a surface layer deposited on at least a surface thereof by plasma polymerisation to increase the hydrophilic nature of the surface.
  • the process further includes providing a cell culture medium including a source of animal cells; and a serum component including an adhesive protein; and contacting the biomedical implant with the cell culture medium.
  • biomedical implants may further be used for the attachment and growth of animal cells in vitro.
  • a biomedical implant including a first polymeric article formed from a bulk polymer material; said first polymeric article bearing a surface layer deposited on at least a surface thereof by plasma polymerisation to increase the hydrophilic nature of the surface;and implanting the biomedical implant into the animal.
  • the second surface layer of the biomedical implant is contacted with a serum component including an adhesive protein. More preferably the serum component is selected from fibronectin, vitronectin, thrombospondin or adhesive fragments thereof.
  • Figure 1 is a schematic view of a system showing an embodiment of the process of this invention.
  • Figures la, lb, lc and Id show different possibilities of placement of the bulk polymeric material in the electric discharge zone, and the multilayer structures thus obtained.
  • Figure 2 is a schematic view of a system showing another embodiment of the process of this invention.
  • Figure 3 is a schematic cross-section of a multilayer polymeric material produced according to this invention.
  • Figure 4 is a schematic cross-section of another multilayer polymeric material produced according to this invention.
  • Figure 5 is a schematic cross-section of yet another multilayer polymeric material produced according to this invention.
  • Figure 6 is a schematic cross-section of still another multilayer polymeric material produced according to this invention.
  • Figure 7 is a schematic cross-section showing an embodiment of the process of this invention using streams of at least two vapours.
  • Figure 8 is a schematic cross-section showing another embodiment of the process of this invention using streams of at least two vapours.
  • Figure 9 illustrates the difference in morphology of human umbilical artery endothelial cells cultured for e days on tissue culture polystyrene (panel a) or fibronectin-coated tissue culture plastic (panel b), on Example 9 (panel c) or Example 9 precoated with Fibronectin (panel d) , Example 12 (panel 3) or Example 12 precoated with fibronectin (panel f), Example 13 (panel g) or Example 13 precoated with fibronectin (panel h) , Example 14 precoated with fibronectin (panel 1) and Example 15 precoated with fibronectin (panel j).
  • this invention utilizes the technique of plasma polymerization for production of multilayer polymeric material.
  • the multilayer polymeric material of this invention consists of a bulk polymeric material 1 and a thin organic-polymeric layer 2.
  • the bulk p ⁇ lymeric material 1 may be of any desired shape and size suitable for the intended application of the finished article.
  • the bulk polymeric material 1 is fashioned into the desired shape of the finished article prior to application of the process of this invention. It is desirable to arrange the geometry of the electric discharge zone such that all desired surfaces of the bulk polymeric material 1 are coated effectively and uniformly with the thin layer 2.
  • any one of the known polymeric materials such as polytetrafluoroethylene, polyethylene, polyesters, polyurethanes, etc., may be used for the bulk polymeric material 1 because the process of this invention can proceed without regard for the composition of the bulk polymeric material 1 and in all cases substantially improved wettability of the treated surfaces is obtained.
  • the invention is particularly applicable to the perfluorinated polymeric materials such as polytetrafluoroethylene.
  • the thin layer 2 of this invention is formed by the plasma polymerization method, a method for deposition of thin layers onto surfaces exposed to the constituents of the vapour phase activated by the electric discharge.
  • the polymerization is performed by introducing vapour comprising one or more organic compounds, henceforth called the monomer vapour, into an electric discharge region.
  • the monomer vapour is directly electrically dissociated and the partially ionized vapour brings about the formation of a polymeric layer 2 on the exposed surfaces of the bulk polymeric material 1.
  • Plasma polymer layers are known in the art to present a uniform, defect free surface to the environment as a result of the molecular nature of the layer formation.
  • the plasma polymerization method is thus a uniquely suitable coating method for formation of a thin "skin" layer that enables the multilayer polymeric material to retain the mechanical properties of the bulk polymeric material while uniformly presenting the chemical groups of the plasma polymer film to the environment.
  • the inadequate, adhesion between the bulk 1 and the thin layer 2 that often is obtained with conventional coating methods based on solvent coating, is overcome in the plasma process because the bulk polymeric material 1 and the thin plasma polymer layer 2 are connected by covalent bonds across the interface.
  • the high cohesion and extensively crosslinked structure of plasma polymer films prevent rotational reorientation of the structure of the plasma polymer and thereby prevent re-emergence of the original surface of the bulk polymeric material, which remains buried underneath the mechanically strong plasma polymer thin layer.
  • vapour composition and the plasma conditions together determine the composition and properties of the thin layer 2.
  • the present invention also prescribes a novel composition for the monomer vapour suitable for the plasma process of this invention.
  • One component of the vapour phase of this invention may include vapour of a saturated alcohol or amine compound.
  • the vapour phase of this invention also may include a mixture of vapours of several saturated alcohol or amine compounds and optionally other organic compounds.
  • the monomer vapour is mixed with an inorganic gas.
  • the vapour from a single alcohol or amine compound may be used. Alternatively, several vapour streams from different compounds may be mixed.
  • saturated compounds examples include methanol, ethanol, propanol, methylamine, ethylamine, propylamine, etc., and generally any compound of the structure R-OH or R-NH 2 where R is a saturated alkyl group, R may optionally contain one or several halogen atoms, amine groups, etc.
  • organic compounds may optionally be used in the vapour phase of the invention, to give a mixed monomer vapour, provided that at least one of the compounds in the mixed vapour phase of the invention is a saturated alcohol or amine compound.
  • an inorganic gas is added to the organic monomer vapour phase.
  • the inorganic gas useful for assisting the plasma process and controlling the resultant thin layer composition include oxygen, argon, hydrogen, etc.
  • Inorganic vapours, in particular water vapour, are, however, not essential in this invention.
  • vapour of more than one chemical compound When vapour of more than one chemical compound is used in the process of the invention, the mixing of vapours can be done in several ways.
  • the streams of two or more vapour and gas components may be united prior to reaching the electric discharge zone in an embodiment as shown in Figure 1.
  • at least one of the streams passes through an electric discharge zone and becomes excited by partial ionization, while at least one other stream does not pass through a discharge zone and is admixed in an unexcited state to the other excited vapour stream, and the mixture is then directed to the bulk polymeric material 1 for thin layer formation, as shown in Figures 7 and 8.
  • any combination is possible provided at least one vapour becomes electrically excited.
  • the thin layer produced by plasma polymerization from a monomer vapour containing vapour of at least one saturated alcohol compound and optionally other organic compounds and/or inorganic gases has an excellent wettability by polar solvents (hydrophilicity) and effects a permanent modification of the surface of the bulk polymeric material 1 by the application of the second layer which is stable with time and does not swell.
  • the multilayer polymeric materials of the invention thus retain good mechanical and other bulk properties while exhibiting improved and permanent wettability in hydrophilic environments.
  • FIG. 1 is a schematic view showing the essential parts of a plasma polymerization apparatus 3 for performing the process of this invention.
  • a vacuum chamber 4 is evacuated by a pumping system 5 connected by an adjustable throttle valve 6 and an exhaust pipe 7.
  • the pressure in the chamber is monitored by a pressure gauge 8.
  • Vapour and gas streams are supplied to a mixing device 9 and reach the vacuum chamber 4 via an inlet pipe 10.
  • Organic monomer liquids are stored in thermostatted containers 11. Evaporation by boiloff supplies organic vapour. Inorganic gases, such as argon and oxygen, are supplied from cylinders 12. All streams are individually controlled by flow control equipment 13 prior to reaching the mixing device 9. All streams may be used singly or in any combination.
  • High frequency electric power is provided by a source 14 via a matching network 15 to the electrodes 16. On application of electric power a discharge is established in the discharge zone 18 between the electrodes and the vapour activated. From the gas plasma the activated products of organic monomer or monomers are polymerized as a thin layer 2 on to one or multiple surfaces of the bulk polymeric material 1.
  • FIG 2 is a schematic view of a modification of the process of this invention.
  • the apparatus is the same as in Figure 1 except that the high frequency electric power is supplied to a coil 17 and no electrodes are provided.
  • Figures 3 to 6 schematically show several embodiments of the multilayer polymeric products of this invention.
  • Figures 3 to 5 show a surface layer 2 applied to one or several faces of a bulk polymeric material 1 of rectangular cross-section.
  • Figure 6 shows a schematic cross-section through a tube-shaped bulk polymeric material 1 that has a thin plasma polymer layer 2 both on the inside and the o outside. _
  • FIG 7 is a schematic view of an embodiment of the process of this invention using two streams of vapour or gas.
  • Each of the streams may direct one or several vapour components to the vacuum chamber via its inlet pipe.
  • the organic vapours and inorganic gases are controlled and mixed prior to the inlet pipe.
  • One of the two streams is fed through the electric discharge zone 18 and the other stream is added to the vacuum chamber downstream of the discharge zone.
  • Figure 8 shows another embodiment of the process where one vapour stream is activated by a coil 17.
  • the process of the invention is not restricted to the particular embodiments shown; three or more inlet pipes may be provided. Examples of the multilayer polymeric materials of this invention will be explained below together with comparative examples. Comparative Examples 1 to 4
  • Comparative example 1 was untreated sheeting of polytetrafluoroethylene. Comparative examples 2 to 4 were prepared using an apparatus as shown in Figure 1 by plasma treatment according to the prior art, that is, with no saturated alcohol vapour provided. Only air was supplied to the vacuum chamber via the flow control 13. Exposure to a plasma of an air atmosphere produces the oxidative plasma treatment known in the art. For example 2 the pressure in the chamber was 0.70 Torr and the density of the applied
  • Multilayer polymeric materials were prepared using the apparatus as shown in Figure 1. Sheet material of polytetrafluoroethylene was used as the bulk polymeric material 1 and attached to the electrodes as in Figure la. Vapour of ethanol (absolute, BDH Chemicals) was supplied by evaporation from the liquid held in a container. Before ignition of the plasma, the vapour was pumped through the reactor and system for several minutes. Plasma polymer layers 2 were then deposited from ethanol vapour onto the surface of the bulk material 1 to a thickness of the layer 2 in the range of 50 to 500 n . Sample 5 was prepared under
  • Sample 6 was prepared under the conditions 0.76 Torr, power density 1.06 W/cm and duration 40 seconds. Sample 6 was prepared under the conditions 0.76 Torr, power density 1.06 W/cm and duration 40 seconds. Sample 6 was prepared under the conditions 0.76 Torr, power density 1.06 W/cm and duration 40 seconds. Sample 6 was prepared under the conditions 0.76 Torr, power density 1.06 W/cm and duration 40 seconds. Sample 6 was prepared under the conditions 0.76 Torr, power density 1.06 W/cm and duration 40 seconds. Sample 6 was prepared under the conditions 0.76 Torr, power density 1.06 W/cm and duration 40 seconds. Sample 6 was prepared under the conditions 0.76 Torr, power density 1.06 W/cm and duration 40 seconds. Sample 6 was prepared under the conditions 0.76 Torr, power density 1.06 W/cm and duration 40 seconds. Sample 6 was prepared under the conditions 0.76 Torr, power density 1.06 W/cm and duration 40 seconds. Sample 6 was prepared under the conditions 0.76 Torr, power density 1.06 W/cm and duration 40 seconds. Sample 6 was prepared
  • Sample 7 was prepared under the conditions 0.50
  • Plasma polymerisation was performed as in examples 5 to 7, but with a vapour source of 96% ethanol and 4% water ⁇ (spectroscopic grade 96% ethanol, Aldrich) .
  • Sample 8 was prepared under the conditions 0.60 Torr, power density 0.84
  • Comparative example 9 was untreated sheet material of
  • Comparative examples 10 and 11 were prepared from FEP sheet material by plasma treatment according to the prior art, as in examples 2 to 4, that is, with no saturated alcohol vapour provided. For example 10, air was supplied to the vacuum chamber via
  • Treatment duration was 30 seconds.
  • the pressure was 0.625 Torr
  • Multilayer polymeric materials were prepared with an
  • vapour of isobutyl alcohol (BDH Chemicals, AnalaR grade) was supplied. Before ignition of the plasma, the vapour was pumped through the reactor and system for several minutes . Plasma polymer layers 2 were then deposited onto the surface of the bulk material 1 to a thickness of the layer 2 in the range of 50 to 500 nm, under conditions in the same range as those used in examples 5 to 8. The receding contact angles of several drops of distilled water on each sample were measured in the same way as for the comparative examples. The results are listed in Table 3.
  • Examples 9 and 12 to 15 were used in experiments involving attachement and growth of human endothelial cells. Results showed that the hydrophilic layer 2 strongly promoted the attachment and growth of the cells.
  • Examples 16 to 18 Multilayer polymeric materials were prepared with an apparatus as shown in Figure 1 and using sheet material of polytetrafluoroethylene as the bulk polymeric material 1 attached to the electrodes. For examples 16 to 18, vapour of methanol (BDH Chemicals, AnalaR grade) was supplied. Plasma polymer layers 2 were then deposited onto the surface of the bulk material 1 to a thickness of the layer 2 in the range of 50 to 500 nm, under conditions in the same range as those used in the previous examples. The receding contact angles of several drops of distilled water on each sample were measured in the same way as for the comparative examples. The results are listed in Table 4.
  • Comparative example 19 was a sheet of poly-dimethylsiloxane (Silastic ) washed in a mixture of n-hexane and methylene chloride, but not plasma treated. Its receding contact angle is listed in Table 5. Examples 20 and 21
  • Multilayer polymeric materials were prepared with an apparatus as shown in Figure 1 and using sheet material of Silastic , washed as in example 19, as the bulk polymeric material 1 attached to the electrodes. Vapor of ethanol (absolute, BDH Chemicals) was supplied. Plasma polymer layers 2 were then deposited onto the surface of the bulk material 1 to a thickness of the layer 2 in the range of 50 to 500 nm, under conditions in the same range as those used in the previous examples. The receding contact angles of several drops of distilled water on each sample were measured in the same way as for the comparative example. The results are listed in Table 5.
  • Example 22 The results are listed in Table 5.
  • Multilayer polymeric materials were prepared with an apparatus as shown in Figure 1 and using as the bulk material 1 polytetrafluoroethylene sheet attached to the electrodes as in Figure la.
  • Vapour of heptylamine (Fluka purum grade) was supplied by evaporation from the liquid held in a container. Before ignition of the plasma, the vapour was pumped through the reactor and system for several minutes.
  • Plasma polymer layer 2 were then deposited onto the surface of the bulk material 1 to a thickness of 50 to 500 nm under a pressure of 0.50 Torr, a power density of 0.9 w/cm2 and durations 2 minutes. Receding contact angles (RCA) of several drops of distilled water were measured in the same way as for the previous examples. The results are listed in Table 5.
  • Multilayer polymeric materials were prepared with an apparatus as shown in Figure 1 and using as the bulk material 1 a multilayer structure consisting of a polyimide film and a Co influenceCr layer applied by evaporation on one side of the polyimide film.
  • the Co_Cr layer was on the side opposite to the electrode and the plasma polymer layer 2 was applied on top of the Co_Cr layer by supplying vapour of ethanol (absolute, BDH Chemicals).
  • the plasma polymer layer 2 was deposited to a thickness of the layer 2 of 40 nm, under conditions in the same range of those used in the previous examples. By applying the plasma polymer layer onto a metal film, a brilliant colour due to interference was obtained. Drops of water were then applied onto the finished multilayer material as in the standard contact angle measurement method.
  • Adhesion testing was done by the standard sticky tape test. In no case was detachment of the thin layer observed, proving that a permanent and strong interfacial bond had been produced between the bulk material and the thin layer.
  • General understanding of the plasma polymerisation process suggests covalent bonding across the interface. Such bonding is superior in strength and durability to the bonding of polar nature (van der Waals forces) obtained by alternative processes for deposition of the thin layer.
  • HUAE cells human endothelial cells derived from umbilical arteries
  • the samples were prepared for cell attachment assays by sonication in a solution of 70% Ethanol at 24 urn for 20 seconds per sample, then rinsed in sterile phosphate-buffered saline solution. Samples were then transferred to serum-free McCoys culture medium for equilibration (at least 1 hr incubation) prior to commencing the cell assay. The modified surface of the film was exposed to the cells in the assay.
  • the cells were routinely maintained in a growth medium consisting of an equal mixture of McCoy 5A (modified) (csL laboratories, Melbourne) and BM86-Wissler (Boehringer-Mannheim) media supplemented with 30% v/v foetal bovine serum (Cytosystems, Sydney), 40 ng/ml fibroblast growth factor (Biomedical Technologies Inc.), 60 ug/ml endothelial cell growth supplement (Collaborative Research), 20 ug/ml insulin (GIBCO), 60 ug/ml penicilin (Glaxo) and 100 ug/ml streptomycin (Glaxo) .
  • McCoy 5A modified
  • BM86-Wissler Boehringer-Mannheim
  • a cell culture medium that contained a serum component was used to assist the JUAE cells to become attached onto either TCP or any of the multilayer polymeric articles according to the present invention.
  • the suitability of the multilayer polymeric articles according to the present invention for cell attachment was determined both in culture medium containing serum and also where the surfaces had also been precoated with serum Fn purified from bovine serum. Coating with Fn was achieved by incubating the flasks with 5 ml solution of 40 ug/ml Fn in PBS at 37°C for 1 hr prior to cell seeding. Excess solution was removed before cells were added.
  • Fn-coated TCP was also included as a control surface, as this surface is known to support good HUAE cell attachment and growth, and the HUAE cells were rountinely maintained on Fn-coated TCP.
  • the morphology of the attached cells when attached to multilayer polymeric articles according to the present invention was taken as an important indicator of the suitability of the surfaces for cell attachment and growth, as only hydrophilic surfaces that do permit HUAE cells to spread well also permit good cell growth.
  • the HUAE cells failed to attach to Example 9, the unmodified FEP film. Furthermore, HUAE cells failed to attach to Example 9 film which had been precoated with Fn. Thus any cell attachment that occurred to Examples 12, 13, 14 or 15, whether with or without precoating with purified Fn, would indicate that the multilayer polymeric articles according to the present invention was more suitable for cell attachment than the unmodified surface.
  • the morphology of the HUAE cells was determined after
  • the multilayer polymeric articles according to the present invention support human endothelial cell attachment, spreading and growth preferably when the culture medium includes serum components such as fibronectin or vitronectin.
  • the materials are therefore suitable for inclusion as components in implants where where good cell interactions with the surface is required, and for use in in vitro cell culture applications.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Organic Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Genetics & Genomics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Biotechnology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Cell Biology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Botany (AREA)
  • Polymers & Plastics (AREA)
  • Biochemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials For Medical Uses (AREA)

Abstract

Un matériau polymère multicouche comprend une première couche d'un matériau polymère en vrac ainsi qu'au moins une seconde couche déposée par polymérisation au plasma sur au moins une surface de la première couche polymère afin d'accroître la nature hydrophile de ladite surface.
PCT/AU1989/000220 1988-05-17 1989-05-17 Materiaux polymeres multicouches non gonflants hydrophiles et leur procede de fabrication WO1989011500A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPI8272 1988-05-17
AUPI827288 1988-05-17

Publications (1)

Publication Number Publication Date
WO1989011500A1 true WO1989011500A1 (fr) 1989-11-30

Family

ID=3773091

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1989/000220 WO1989011500A1 (fr) 1988-05-17 1989-05-17 Materiaux polymeres multicouches non gonflants hydrophiles et leur procede de fabrication

Country Status (1)

Country Link
WO (1) WO1989011500A1 (fr)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0633031A1 (fr) * 1993-06-24 1995-01-11 Siemens Aktiengesellschaft Composition et procédé d'application de revêtements anti-salissure sur dispositifs medicaux
WO1996030060A1 (fr) * 1995-03-28 1996-10-03 Aortech Europe Ltd. Dispositif medical traite avec une composition polymere hydrophile
EP0747069A2 (fr) * 1995-06-07 1996-12-11 Cook Incorporated Dispositif médical implantable
WO1997031034A1 (fr) * 1996-02-21 1997-08-28 Commonwealth Scientific And Industrial Research Organisation Procede de reduction de la fissuration dans une matiere plastique
WO1998017331A1 (fr) * 1995-06-07 1998-04-30 Cook Incorporated Dispositif medical implantable et contenant de l'argent
WO1998028026A1 (fr) * 1996-12-23 1998-07-02 Novartis Ag Revetements reactifs
US5824049A (en) * 1995-06-07 1998-10-20 Med Institute, Inc. Coated implantable medical device
US5874165A (en) * 1996-06-03 1999-02-23 Gore Enterprise Holdings, Inc. Materials and method for the immobilization of bioactive species onto polymeric subtrates
US5897955A (en) * 1996-06-03 1999-04-27 Gore Hybrid Technologies, Inc. Materials and methods for the immobilization of bioactive species onto polymeric substrates
US5916585A (en) * 1996-06-03 1999-06-29 Gore Enterprise Holdings, Inc. Materials and method for the immobilization of bioactive species onto biodegradable polymers
AU712565B2 (en) * 1996-02-21 1999-11-11 Commonwealth Scientific And Industrial Research Organisation Method for reducing crazing in a plastics material
US6299604B1 (en) 1998-08-20 2001-10-09 Cook Incorporated Coated implantable medical device
WO2003035850A1 (fr) * 2001-10-26 2003-05-01 Celltran Limited Substrat pour transfert cellulaire
US6774278B1 (en) 1995-06-07 2004-08-10 Cook Incorporated Coated implantable medical device
US6923978B2 (en) 1992-09-14 2005-08-02 Novartis Ag Multilayer materials
EP1750155A1 (fr) * 2005-08-01 2007-02-07 ibidi GmbH Chambre d'échantillon et procédé pour sa fabrication
EP2147971A3 (fr) * 2008-07-25 2010-04-28 Becton, Dickinson & Company Surfaces définies de culture de cellules et procédés d'utilisation
US7862605B2 (en) 1995-06-07 2011-01-04 Med Institute, Inc. Coated implantable medical device

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3387991A (en) * 1964-10-13 1968-06-11 Rexall Drug Chemical Glow discharge polymerization coating of polyolefin surfaces to render them receptive to adhesives, inks, and the like
AU1848167A (en) * 1966-03-11 1968-09-05 Radiation Research Corporation Method of grafting ethylenically unsaturated monomer toa polymeric substrate
US3449154A (en) * 1965-09-07 1969-06-10 Gaf Corp Poly-alpha-olefins coated with lactams or lactones and methods for producing same
GB2101608A (en) * 1981-06-22 1983-01-19 Shinetsu Chemical Co Method for treating a shaped article of a vinyl chloride-based resin
JPS58217526A (ja) * 1982-06-14 1983-12-17 Sumitomo Bakelite Co Ltd プリント基板用銅張積層品の製造方法
EP0133832A1 (fr) * 1983-07-29 1985-03-06 Electricite De France Procédé et dispositif de réalisation d'un revêtement polymérisé sur un substrat
JPS60158231A (ja) * 1984-01-30 1985-08-19 Agency Of Ind Science & Technol 重合体の表面処理方法
JPS6259637A (ja) * 1985-09-11 1987-03-16 Mitsui Petrochem Ind Ltd 接着性の改良方法
JPS6289737A (ja) * 1985-06-27 1987-04-24 Nippon Medical Supply Corp プラスチツクチユ−ブの製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3387991A (en) * 1964-10-13 1968-06-11 Rexall Drug Chemical Glow discharge polymerization coating of polyolefin surfaces to render them receptive to adhesives, inks, and the like
US3449154A (en) * 1965-09-07 1969-06-10 Gaf Corp Poly-alpha-olefins coated with lactams or lactones and methods for producing same
AU1848167A (en) * 1966-03-11 1968-09-05 Radiation Research Corporation Method of grafting ethylenically unsaturated monomer toa polymeric substrate
GB2101608A (en) * 1981-06-22 1983-01-19 Shinetsu Chemical Co Method for treating a shaped article of a vinyl chloride-based resin
JPS58217526A (ja) * 1982-06-14 1983-12-17 Sumitomo Bakelite Co Ltd プリント基板用銅張積層品の製造方法
EP0133832A1 (fr) * 1983-07-29 1985-03-06 Electricite De France Procédé et dispositif de réalisation d'un revêtement polymérisé sur un substrat
JPS60158231A (ja) * 1984-01-30 1985-08-19 Agency Of Ind Science & Technol 重合体の表面処理方法
JPS6289737A (ja) * 1985-06-27 1987-04-24 Nippon Medical Supply Corp プラスチツクチユ−ブの製造方法
JPS6259637A (ja) * 1985-09-11 1987-03-16 Mitsui Petrochem Ind Ltd 接着性の改良方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DERWENT ABSTRACT ACCESSION NO. 86-077671/12, Class P42; & JP,A,60 158 231 (Agency of Ind. Sci. Tech.), 19 August 1985 (19.08.85). *
DERWENT ABSTRACT ACCESSION NO. 87-113207/16, Class A17; & JP,A,62 059 637 (Mitsui Petrochem Ind. K.K.), 16 March 1987 (16.03.87). *
PATENT ABSTRACTS OF JAPAN, C-215, page 145; & JP,A,58 217 526 (Sumitomo Bakelite K.K.), 17 December 1983, (17.12.83). *
PATENT ABSTRACTS OF JAPAN, C-448, page 126; & JP,A,62 089 737 (Nippon Medical Supply Corp), 24 April 1987 (12.04.87). *

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6923978B2 (en) 1992-09-14 2005-08-02 Novartis Ag Multilayer materials
EP0633031A1 (fr) * 1993-06-24 1995-01-11 Siemens Aktiengesellschaft Composition et procédé d'application de revêtements anti-salissure sur dispositifs medicaux
WO1996030060A1 (fr) * 1995-03-28 1996-10-03 Aortech Europe Ltd. Dispositif medical traite avec une composition polymere hydrophile
US6774278B1 (en) 1995-06-07 2004-08-10 Cook Incorporated Coated implantable medical device
EP0747069A2 (fr) * 1995-06-07 1996-12-11 Cook Incorporated Dispositif médical implantable
EP0747069A3 (fr) * 1995-06-07 1998-01-07 Cook Incorporated Dispositif médical implantable
WO1998017331A1 (fr) * 1995-06-07 1998-04-30 Cook Incorporated Dispositif medical implantable et contenant de l'argent
US7862605B2 (en) 1995-06-07 2011-01-04 Med Institute, Inc. Coated implantable medical device
US5824049A (en) * 1995-06-07 1998-10-20 Med Institute, Inc. Coated implantable medical device
US5873904A (en) * 1995-06-07 1999-02-23 Cook Incorporated Silver implantable medical device
GB2326165B (en) * 1996-02-21 2000-08-09 Commw Scient Ind Res Org Method for reducing crazing in a plastics material
AU712565B2 (en) * 1996-02-21 1999-11-11 Commonwealth Scientific And Industrial Research Organisation Method for reducing crazing in a plastics material
GB2326165A (en) * 1996-02-21 1998-12-16 Commonwealth Scientific And Industrial Research Organization Method for reducing crazing in a plastics material
WO1997031034A1 (fr) * 1996-02-21 1997-08-28 Commonwealth Scientific And Industrial Research Organisation Procede de reduction de la fissuration dans une matiere plastique
US5897955A (en) * 1996-06-03 1999-04-27 Gore Hybrid Technologies, Inc. Materials and methods for the immobilization of bioactive species onto polymeric substrates
US5914182A (en) * 1996-06-03 1999-06-22 Gore Hybrid Technologies, Inc. Materials and methods for the immobilization of bioactive species onto polymeric substrates
US5916585A (en) * 1996-06-03 1999-06-29 Gore Enterprise Holdings, Inc. Materials and method for the immobilization of bioactive species onto biodegradable polymers
US5874165A (en) * 1996-06-03 1999-02-23 Gore Enterprise Holdings, Inc. Materials and method for the immobilization of bioactive species onto polymeric subtrates
US6436481B1 (en) 1996-12-23 2002-08-20 Novartis Ag Method of producing a reactive coating by after-glow plasma polymerization
WO1998028026A1 (fr) * 1996-12-23 1998-07-02 Novartis Ag Revetements reactifs
US6299604B1 (en) 1998-08-20 2001-10-09 Cook Incorporated Coated implantable medical device
US6730064B2 (en) 1998-08-20 2004-05-04 Cook Incorporated Coated implantable medical device
WO2003035850A1 (fr) * 2001-10-26 2003-05-01 Celltran Limited Substrat pour transfert cellulaire
EP2261718A3 (fr) * 2005-08-01 2011-03-09 ibidi GmbH Chambre d'échantillon et procédé pour sa fabrication
EP1750155A1 (fr) * 2005-08-01 2007-02-07 ibidi GmbH Chambre d'échantillon et procédé pour sa fabrication
WO2007014739A1 (fr) * 2005-08-01 2007-02-08 Ibidi Gmbh Chambre d'echantillonnage et procede de production de cette chambre
US8470110B2 (en) 2005-08-01 2013-06-25 Ibidi Gmbh Sample chamber and method for the production thereof
EP2147971A3 (fr) * 2008-07-25 2010-04-28 Becton, Dickinson & Company Surfaces définies de culture de cellules et procédés d'utilisation
US8288513B2 (en) 2008-07-25 2012-10-16 Becton, Dickinson And Company Defined cell culturing surfaces and methods of use
EP2213728A1 (fr) * 2008-07-25 2010-08-04 Becton, Dickinson & Company Surfaces définies de culture de cellules et procédés d'utilisation
US8728818B2 (en) 2008-07-25 2014-05-20 Corning Incorporated Defined cell culturing surfaces and methods of use
US8916382B2 (en) 2008-07-25 2014-12-23 Corning Incorporated Defined cell culturing surfaces and methods of use
US9157059B2 (en) 2008-07-25 2015-10-13 Corning Incorporated Defined cell culturing surfaces and methods of use
CN106148189A (zh) * 2008-07-25 2016-11-23 康宁有限公司 限定的细胞培养表面及其使用方法
EP3323883A1 (fr) * 2008-07-25 2018-05-23 Corning Incorporated Surfaces définies de culture de cellules et procédés d'utilisation

Similar Documents

Publication Publication Date Title
WO1989011500A1 (fr) Materiaux polymeres multicouches non gonflants hydrophiles et leur procede de fabrication
US5449383A (en) Cell growth substrates
Förch et al. Recent and expected roles of plasma‐polymerized films for biomedical applications
Griesser et al. Growth of human cells on plasma polymers: putative role of amine and amide groups
EP1740950B1 (fr) Immobilisation de biomolecule au moyen d'une technologie au plasma atmospherique
Ratner Plasma deposition for biomedical applications: a brief review
Harsch et al. Pulsed plasma deposition of allylamine on polysiloxane: a stable surface for neuronal cell adhesion
Porté‐Durrieu et al. Development of RGD peptides grafted onto silica surfaces: XPS characterization and human endothelial cell interactions
Ratner Surface modification of polymers: chemical, biological and surface analytical challenges
Lahann et al. Reactive polymer coatings: A platform for patterning proteins and mammalian cells onto a broad range of materials
Haddow et al. Plasma‐polymerized surfaces for culture of human keratinocytes and transfer of cells to an in vitro wound‐bed model
US6432510B1 (en) Fluorinated resins having a surface with high wettability
Johnson et al. Biocompatibility studies on plasm polymerized interface materials encompassing both hydrophobic and hydrophilic surfaces
US20060051522A1 (en) Method of pulsed laser assisted surface modification
Kottk–Marchant et al. Human endothelial cell growth and coagulant function varies with respect to interfacial properties of polymeric substrates
Sergeeva et al. What is really driving cell–surface interactions? Layer-by-layer assembled films may help to answer questions concerning cell attachment and response to biomaterials
Bouaziz et al. Vascular endothelial cell responses to different electrically charged poly (vinylidene fluoride) supports under static and oscillating flow conditions
AU7844098A (en) Non-fouling, wettable coated devices
Ibrahim et al. Atmospheric pressure dielectric barrier discharges for the deposition of organic plasma polymer coatings for biomedical application
Kim et al. Preparation of insulin-immobilized polyurethanes and their interaction with human fibroblasts
US5010009A (en) Material for cell attachment and growth
AU640345B2 (en) Hydrophilic non-swelling multilayer polymeric materials and process for their manufacture
US5002652A (en) Plasma polymerized polysiloxane membrane
Kugo et al. Fibroblast attachment to Arg-Gly-Asp peptide-immobilized poly (γ-methyl L-glutamate)
Mitev et al. PECVD polymerised coatings on thermo-sensitive plastic support

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU DK FI JP KR NO US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1989906320

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1989906320

Country of ref document: EP