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WO2002077073A2 - Plastic articles having a polyphosphazene coating - Google Patents

Plastic articles having a polyphosphazene coating Download PDF

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Publication number
WO2002077073A2
WO2002077073A2 PCT/EP2002/003268 EP0203268W WO02077073A2 WO 2002077073 A2 WO2002077073 A2 WO 2002077073A2 EP 0203268 W EP0203268 W EP 0203268W WO 02077073 A2 WO02077073 A2 WO 02077073A2
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WO
WIPO (PCT)
Prior art keywords
coating
plastic
plastic substrate
polymer
adhesion promoter
Prior art date
Application number
PCT/EP2002/003268
Other languages
French (fr)
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WO2002077073A3 (en
Inventor
Michael Grunze
Dsidra Tur
Alexander Pertsin
Original Assignee
Polyzenix Gmbh
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 Polyzenix Gmbh filed Critical Polyzenix Gmbh
Priority to AU2002310973A priority Critical patent/AU2002310973A1/en
Publication of WO2002077073A2 publication Critical patent/WO2002077073A2/en
Publication of WO2002077073A3 publication Critical patent/WO2002077073A3/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
    • C09D185/02—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers containing phosphorus

Definitions

  • the present invention relates to plastic articles having a coating which comprises polyphosphazene derivatives, a process for their production as well as the use as a wound coverage having excellent biological and pharmaceutical properties.
  • the coating of plastics with other plastics has been hitherto achieved with a variety of plastics, especially with the aim, on the one hand, to maintain the properties of the plastics which serve as a substrate, and, on the other hand, to change and to optimise the surface properties of said plastics by applying a coating comprised of another plastic, on the surface thereof.
  • problems may arise, particularly based on the chemical and physical behaviour and the adhesion of the different plastics among each other.
  • miscibility gaps might be created from co-extrusion of two different plastics, which gives the desired arrangement of the plastics - i.e. one plastic as the substrate strictcore", and another plastic used for coating applied on the substrate, but in this case the adhesion of the plastics among each other is negatively affected.
  • plastics from solvents i.e. plastics in solution
  • reasons, not trivial as well and there must be carried out a huge amount of series of experiments to find appropriate solvents and solvent systems which, on the one hand, do not or substantially not change the properties of the plastic which serves as substrate, for example to maintain the desired elasticity, and, on the other hand, to solve the other plastic which is used for coating or for modifying the surface.
  • a lot of effort is necessary when a strong adhesion of different plastics among each other should be achieved, since the evaporation of the solvent might result in the phenomenon of phase separation, and thereby the loss of a permanent and durable adhesion might arise.
  • the coating of plastics is desirable, since the plastics used for the coating often exhibit properties which cannot be achieved with the hitherto used and above mentioned plastics.
  • the polymeric compound poly[bis(trifluoroethoxy)phosphazene] exhibits good antithrombogenic action as a filler (see Tur, füren zur Thrombenresistenz von Poly[bis(trifluoroethoxy)phosphazen] [Studies of resistance of poly[bis(trifluoroethoxy)phosphazene] to thrombus formation] and Hollemann Wiberg, "Stickstoff für Phosphors" [Nitrogen compounds of phosphorus], Lehrbuch der anorganischen Chemie [Textbook of Inorganic Chemistry], 666-669, 91st-100th Edition, Walter de Gruyter Verlag, 1985; and Tur, Vinogradova et al., "Entwicklungstendenzen bei polymeranalogen tighten von Polyphosphazenen” [Trends in development of polymer-like reactions of polyphosphazenes], Acta Polymerica 39, No. 8, 424-429 (1988)). Further, polyphosphazen
  • the known coating methods are not suitable for applying polyphoshazene derivatives, particularly poly[bis(trifluoroethoxy)phosphazene] on the surface of common plastics and thereby imparting said plastic surfaces and the articles made therefrom the positive and desirable properties of said polyphosphazene derivatives.
  • the polyphosphazene derivatives mentioned in DE 196 13 048 can be prepared only with a high experimental input, but do not exhibit, as a volume material, the mechanical properties which can be achieved with other plastics, such as hardness etc., and are very expensive due to the preparation method.
  • the technical problem underlying the present invention is to provide a new system and a method for coating commonly used plastics with polyphosphazene derivatives, wherein the coating should not negatively affect the mechanical properties of said plastics used as the substrate, particularly should not change or destroy said properties, and the coating of the polyphosphazene derivative should exhibit a high adhesion and bonding to the plastics used as substrate without negatively affecting or destroying the properties of the polyphosphazene derivative to be used as a constituent of the coating.
  • n is from 2 to ⁇ ,
  • R 1 to R 6 are the same or different and represent an alkoxy, alkylsulfonyl, dialkylamino or aryloxy group, or a heterocycloalkyl or heteroaryl group in which nitrogen is the heteroatom.
  • the coating can be applied to any plastic substrate.
  • the term “antimony oxide” encompasses any commonly used plastic without any particular limitation. Examples of plastic substrates are polyethylene therephthalates, polyurethanes, polyethylenes, polyvinylchlorides and silicones.
  • the term drawnplastic article includes any plastic articles without any particular limitation of the form or shape.
  • said plastic article encompasses artificial implants such as plastic implants for e.g. breast, nose or ear, bone nails, bone screws, bone plates, artificial (urinary) bladder, artificial cartilage, dental implants, artificial bones for e.g. artificial hip or hip joints, artificial esophagus and artificial trachea; artificial (arterial and veinous) blood vessels; stents such as urological stents and cardiovascular stents; catheters such as urological catheters and cardiovascular catheters; cardiovascular grafts; emplastrums; dermatoplasties; devices, e.g.
  • therapeutic devices such as cardiac pacemakers, defibrillators, electrodes for cardiac pace- makers and defibrillators, surgical devices, surgical instruments, artificial biological membrans and artificial organs such as artificial kidneys and artificial heart, and, in a preferred embodiment, wound coverages.
  • the degree of polymerization of the polymer used in the coating according to the present invention can be from 2 to ⁇ . However, the preferred range for the degree of polymerization is from 20 to 200,000, and more preferably 40 to 100,000.
  • At least one of the groups R 1 to R 6 in the polymer used is an alkoxy group substituted with at least one fluorine atom.
  • alkyl groups in the alkoxy, alkylsulfonyl and dialkylamino groups are, for example, straight or branched alkyl groups with 1 to 20 carbon atoms, in which the alkyl groups can, for example, be substituted with at least one halogen atom, such as a fluorine atom.
  • alkoxy groups are the methoxy, ethoxy, propoxy and butoxy groups, which can preferably be substituted with at least one fluorine atom.
  • the 2,2,2- trifluoroethoxy group is particularly preferred.
  • alkylsulfonyl groups are methylsulfonyl, ethylsulfonyl, propylsulfonyl and butylsulfonyl groups.
  • dialkylamino groups are dimethylamino, diethylamino, dipropylamino and dibutyl- amino groups.
  • the aryl group in the aryloxy group is, for example, a compound with one or more aromatic ring systems, in which the aryl group can, for example, be substituted with at least one alkyl group as previously defined.
  • aryloxy groups are the phenoxy and naphthoxy groups and their derivatives.
  • the heterocycloalkyl group is, for instance, a ring system containing 3 to 7 atoms, with at least one ring atom being a nitrogen atom.
  • the heterocycloalkyl group can, for example, be substituted with at least one alkyl group as previously defined.
  • Examples of heterocycloalkyl groups are the piperidinyl, piperazinyl, pyrrolidinyl and morpholinyl groups and their derivatives.
  • the heteroaryl group is, for example, a compound with one or more aromatic ring systems in which at least one ring atom is a nitrogen atom.
  • the heteroaryl group can, for example, be substituted with at least one alkyl group as previously defined.
  • Examples of heteroaryl groups are the pyrrolyl, pyridinyl, pyridinolyl, isoquinolinyl and quinolinyl groups and their derivatives.
  • the coating of the plastic article of the present invention has preferably a thickness ranging from a monolayer comprised of polymer (I) to about 20 ⁇ m, more preferably from about 1 nm to about 10 ⁇ m, and particularly preferably up to about 3 ⁇ m.
  • the coating of the plastic article comprises a 32 P-, 33 P- or As or Sb-isotope labelled poly[bis(trifluoroethoxy)phosphazene].
  • a layer containing an adhesion promoter is provided between the surface of the plastic substrate and the coating containing the polyphosphazene derivative of formula (I).
  • the adhesion promoter or spacer contains a polar end group.
  • a polar end group examples are hydroxy groups, carboxy groups, carboxyl groups, amino groups or nitro groups, but end groups of the O-ED type can also be used, wherein O-ED represents an alkoxy, alkylsulfonyl, dialkylamino or aryloxy group, or a heterocycloalkyl or heteroaryl group in which nitrogen is the heteroatom, and can have different substitutents like halogen atoms, particularly fluorine atoms.
  • the adhesion promoter is, for example, a silicium-organic compound, preferably an amino-terminated silane or based on aminosilane, amino-terminated alkenes, nitro-terminated alkenes and silanes, or an alkylphosphonic acid.
  • Aminopropyltrimethoxysilane is particularly preferred.
  • the adhesion promoter particularly improves adhesion of the coating to the surface of a plastic substrate by coupling the adhesion promoter to the surface of the plastic substrate, for instance by ionic and/or covalent bonds and by further coupling of the adhesion promoter to reactive components, particularly to the above described polymer with the general formula (I) of the coating, for instance, through ionic and/or covalent bonds.
  • step (c) pulling out and drying the plastic substrate coated with said polymer on air or in an inert gas atmosphere.
  • step (a) of the process according to the present invention the plastic substrate to be coated should be degreased in order to provide a good adhesion between the coating and surface of the plastic substrate.
  • the plastic article should be further sterilised.
  • the agents used for degreasing and/or sterilisation should not dissolve or attack the plastic substrate.
  • step (b) the polymer, preferably poly[bis(trifluoroethoxy)polyphosphazene], is dissolved in a suitable solvent in a concentration of from about 0.01 to about 5 g/100 ml, preferably 0.01 to 3 g/100 ml.
  • suitable solvent include acetone, tetrahydrofuran, ethylacetate, methylethylketon, cyclohexanone, hexafluorobenzene and mixtures thereof.
  • the immersion of the plastic substrate into the solution of said polymer can be carried out with any suitable means, for example semi-automatically or automatically, and does not exhibit any limitation.
  • the time period of immersion is dependent on the solvent or solvent mixture used and on the plastic substrate, i.e. the resin constituents, used, and may range from 1 second to several hours, during which the polymer molecules are deposited on the surface of the plastic substrate.
  • the rate of the pulling or drawing out of the coated plastic substrates from the polymer solution is not specifically limited, but may depend on the plastic substrate used and its shape, and on pressure and temperature conditions such as standard pressure and room temperature. For instance, in case of hoses, the rate of pulling out is about 10 cm/min.
  • Drying of the coated plastic substrates is carried out on air or in an inert gas atmosphere, such as argon or nitrogen. The drying can last from about 1 second to several hours, dependent on temperature, solvent, and plastic substrate used.
  • a complete drying of the coated plastic substrates on air or in an inert gas atmosphere is preferred, in order to remove residual solvent, if present. Depending on the plastic substrate and solvent or solvent mixture used, the complete drying may require up to several days. It is also possible to remove the solvent or residual of solvents under vacuum.
  • an adhesion promoter as defined above can be applied to the surface of the plastic substrate prior to step (b) of the process of the present invention.
  • step (b) of the process of the present invention it is also possible to subject the plastic substrate to a plasma treatment prior to step (b) of the process of the present invention in order to improve adhesion of the coating to the surface of the plastic substrate.
  • firstly a plasma treatment and secondly the application of an adhesion promoter can be carried out prior to step (b) of the process of the present invention.
  • the coating of the adhesion promoter can be carried out with any method known in the prior art, such as solvent coating, vapour deposition etc.
  • the plastic article can also be provided with a microstructure in the coating.
  • the sizes of such microstructures do not exhibit any limitation, and can have sizes from a few nanometres up to several micrometers or even more.
  • the microstructures can be applied by any method known in the art, such as photolithography or using electron radiation or ion radiation or using a laser.
  • Microstructures of the coated plastic substrates can also be obtained by using direct ..writing" on the plastic substrates by means of a laser, electron radiation or X-ray.
  • the microstructures can be obtained by so-called melt structuring, in which a thin wire is heated on the melting temperature of the polymer, said wire is melting the desired structure in the plastic substrate by direct contact.
  • melt structuring in which a thin wire is heated on the melting temperature of the polymer, said wire is melting the desired structure in the plastic substrate by direct contact.
  • a specific embodiment of the present invention is a wound coverage comprising at least one layer having a coating containing the above polymer (I), wherein said coating is in contact with the wound such as a burn wound, of a patient in need thereof.
  • the coating which is in contact with the wound of a patient imparts excellent properties such as biobompatibility, anti-inflammatory effects etc. to the wound coverage, which is based on the polymer (I) used in the coating.
  • the wound coverage of the present invention can be built up as a two-layered structure, i.e. the plastic substrate and the coating, or three or more layered structure (..multi-layer structure").
  • the wound coverage of the present invention should be preferably gas( administratair")-permeable, i.e. a porous wound coverage. This is achieved by providing e.g. a porous plastic substrate having pore sizes of from about a few nanometers, e.g. 5 nm, to about 30 ⁇ m, and a coating and optionally further layers which also exhibit pores comparable to the pores of the plastic substrate, for the gas-exchange.
  • a specifically advantageous property of the wound coverage of the present invention is that the freshly formed cellular tissue or fibrous tissue originating from the wound, does not adhere or infiltrate the coating of said wound coverage.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Materials For Medical Uses (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

The present invention relates to plastic articles having a coating which comprises polyphosphazene derivatives, a process for the production as well as the use as a wound coverage, having excellent biocompatible properties.

Description

PLASTIC ARTICLES HAVING A POLYPHOSPHAZENE COATING
The present invention relates to plastic articles having a coating which comprises polyphosphazene derivatives, a process for their production as well as the use as a wound coverage having excellent biological and pharmaceutical properties.
The coating of plastics with other plastics has been hitherto achieved with a variety of plastics, especially with the aim, on the one hand, to maintain the properties of the plastics which serve as a substrate, and, on the other hand, to change and to optimise the surface properties of said plastics by applying a coating comprised of another plastic, on the surface thereof.
In this respect, problems may arise, particularly based on the chemical and physical behaviour and the adhesion of the different plastics among each other. For example, miscibility gaps might be created from co-extrusion of two different plastics, which gives the desired arrangement of the plastics - i.e. one plastic as the substrate („core"), and another plastic used for coating applied on the substrate, but in this case the adhesion of the plastics among each other is negatively affected.
The application of plastics from solvents, i.e. plastics in solution, is, for the above named reasons,, not trivial as well, and there must be carried out a huge amount of series of experiments to find appropriate solvents and solvent systems which, on the one hand, do not or substantially not change the properties of the plastic which serves as substrate, for example to maintain the desired elasticity, and, on the other hand, to solve the other plastic which is used for coating or for modifying the surface. In particular, a lot of effort is necessary when a strong adhesion of different plastics among each other should be achieved, since the evaporation of the solvent might result in the phenomenon of phase separation, and thereby the loss of a permanent and durable adhesion might arise. In particular, such a phenomenon is observed when a coating comprising a fluorine containing plastic such as Teflon, is applied to plastics such as polyethylene therephthalate (PET), polyurethanes (PU), polyethylenes (PE) and polyvinylchlorides (PVC), to change and to optimise their surface properties.
However, the coating of plastics is desirable, since the plastics used for the coating often exhibit properties which cannot be achieved with the hitherto used and above mentioned plastics.
Moreover, there can be achieved a drastic reduction of costs, since the plastics used only for the coating are in many cases more expensive in their production than plastics used as the substrate therefore.
The polymeric compound poly[bis(trifluoroethoxy)phosphazene] exhibits good antithrombogenic action as a filler (see Tur, Untersuchungen zur Thrombenresistenz von Poly[bis(trifluoroethoxy)phosphazen] [Studies of resistance of poly[bis(trifluoroethoxy)phosphazene] to thrombus formation] and Hollemann Wiberg, "Stickstoffverbindungen des Phosphors" [Nitrogen compounds of phosphorus], Lehrbuch der anorganischen Chemie [Textbook of Inorganic Chemistry], 666-669, 91st-100th Edition, Walter de Gruyter Verlag, 1985; and Tur, Vinogradova et al., "Entwicklungstendenzen bei polymeranalogen Umsetzungen von Polyphosphazenen" [Trends in development of polymer-like reactions of polyphosphazenes], Acta Polymerica 39, No. 8, 424-429 (1988)). Further, polyphosphazene is used in German Patent 196 13 048 for coating artificial implants, with the intention to avoid thrombus formation on the surface of the implants, and especially heart walls can be ameliorated by this type of coating.
In the German patent DE 196 13 048, there are mentioned particularly artificial implants. However, the methods cited and proposed therein are not suitable for coating other plastics, since especially by using aggressive chemicals such as persulfuric acid, the mechanical properties of the plastics used as substrates are at least partially negatively affected, when even not destroyed.
Accordingly, the known coating methods are not suitable for applying polyphoshazene derivatives, particularly poly[bis(trifluoroethoxy)phosphazene] on the surface of common plastics and thereby imparting said plastic surfaces and the articles made therefrom the positive and desirable properties of said polyphosphazene derivatives. On the other hand, the polyphosphazene derivatives mentioned in DE 196 13 048 can be prepared only with a high experimental input, but do not exhibit, as a volume material, the mechanical properties which can be achieved with other plastics, such as hardness etc., and are very expensive due to the preparation method.
Therefore, the technical problem underlying the present invention is to provide a new system and a method for coating commonly used plastics with polyphosphazene derivatives, wherein the coating should not negatively affect the mechanical properties of said plastics used as the substrate, particularly should not change or destroy said properties, and the coating of the polyphosphazene derivative should exhibit a high adhesion and bonding to the plastics used as substrate without negatively affecting or destroying the properties of the polyphosphazene derivative to be used as a constituent of the coating.
The above problem is solved by providing a plastic article comprising a plastic substrate and a coating containing a polymer having the following general formula
(I)
Figure imgf000004_0001
wherein n is from 2 to ∞ ,
R1 to R6 are the same or different and represent an alkoxy, alkylsulfonyl, dialkylamino or aryloxy group, or a heterocycloalkyl or heteroaryl group in which nitrogen is the heteroatom. The coating can be applied to any plastic substrate. The term „plastic substrate" encompasses any commonly used plastic without any particular limitation. Examples of plastic substrates are polyethylene therephthalates, polyurethanes, polyethylenes, polyvinylchlorides and silicones.
The term „plastic article" includes any plastic articles without any particular limitation of the form or shape. Examples of said plastic article, but not limited to, encompasses artificial implants such as plastic implants for e.g. breast, nose or ear, bone nails, bone screws, bone plates, artificial (urinary) bladder, artificial cartilage, dental implants, artificial bones for e.g. artificial hip or hip joints, artificial esophagus and artificial trachea; artificial (arterial and veinous) blood vessels; stents such as urological stents and cardiovascular stents; catheters such as urological catheters and cardiovascular catheters; cardiovascular grafts; emplastrums; dermatoplasties; devices, e.g. in the gastrointestinal tract, in the prostata, in the urinary tract, or for the protection of neurons and neurofibers; therapeutic devices such as cardiac pacemakers, defibrillators, electrodes for cardiac pace- makers and defibrillators, surgical devices, surgical instruments, artificial biological membrans and artificial organs such as artificial kidneys and artificial heart, and, in a preferred embodiment, wound coverages.
The degree of polymerization of the polymer used in the coating according to the present invention can be from 2 to ∞. However, the preferred range for the degree of polymerization is from 20 to 200,000, and more preferably 40 to 100,000.
Preferably, at least one of the groups R1 to R6 in the polymer used is an alkoxy group substituted with at least one fluorine atom.
The alkyl groups in the alkoxy, alkylsulfonyl and dialkylamino groups are, for example, straight or branched alkyl groups with 1 to 20 carbon atoms, in which the alkyl groups can, for example, be substituted with at least one halogen atom, such as a fluorine atom. Examples of alkoxy groups are the methoxy, ethoxy, propoxy and butoxy groups, which can preferably be substituted with at least one fluorine atom. The 2,2,2- trifluoroethoxy group is particularly preferred. Examples of alkylsulfonyl groups are methylsulfonyl, ethylsulfonyl, propylsulfonyl and butylsulfonyl groups. Examples of dialkylamino groups are dimethylamino, diethylamino, dipropylamino and dibutyl- amino groups.
The aryl group in the aryloxy group is, for example, a compound with one or more aromatic ring systems, in which the aryl group can, for example, be substituted with at least one alkyl group as previously defined. Examples of aryloxy groups are the phenoxy and naphthoxy groups and their derivatives.
The heterocycloalkyl group is, for instance, a ring system containing 3 to 7 atoms, with at least one ring atom being a nitrogen atom. The heterocycloalkyl group can, for example, be substituted with at least one alkyl group as previously defined. Examples of heterocycloalkyl groups are the piperidinyl, piperazinyl, pyrrolidinyl and morpholinyl groups and their derivatives. The heteroaryl group is, for example, a compound with one or more aromatic ring systems in which at least one ring atom is a nitrogen atom. The heteroaryl group can, for example, be substituted with at least one alkyl group as previously defined. Examples of heteroaryl groups are the pyrrolyl, pyridinyl, pyridinolyl, isoquinolinyl and quinolinyl groups and their derivatives.
The coating of the plastic article of the present invention has preferably a thickness ranging from a monolayer comprised of polymer (I) to about 20 μm, more preferably from about 1 nm to about 10 μm, and particularly preferably up to about 3 μm.
in a preferred embodiment of the present invention, the coating of the plastic article comprises a 32P-, 33P- or As or Sb-isotope labelled poly[bis(trifluoroethoxy)phosphazene]. In one further preferred embodiment of the present invention, a layer containing an adhesion promoter is provided between the surface of the plastic substrate and the coating containing the polyphosphazene derivative of formula (I).
Preferably, the adhesion promoter or spacer, respectively, contains a polar end group. Examples are hydroxy groups, carboxy groups, carboxyl groups, amino groups or nitro groups, but end groups of the O-ED type can also be used, wherein O-ED represents an alkoxy, alkylsulfonyl, dialkylamino or aryloxy group, or a heterocycloalkyl or heteroaryl group in which nitrogen is the heteroatom, and can have different substitutents like halogen atoms, particularly fluorine atoms.
Particularly, the adhesion promoter is, for example, a silicium-organic compound, preferably an amino-terminated silane or based on aminosilane, amino-terminated alkenes, nitro-terminated alkenes and silanes, or an alkylphosphonic acid. Aminopropyltrimethoxysilane is particularly preferred.
The adhesion promoter particularly improves adhesion of the coating to the surface of a plastic substrate by coupling the adhesion promoter to the surface of the plastic substrate, for instance by ionic and/or covalent bonds and by further coupling of the adhesion promoter to reactive components, particularly to the above described polymer with the general formula (I) of the coating, for instance, through ionic and/or covalent bonds.
Furthermore, there is provided a process for coating the above-defined plastic substrates using a polymer having the general formula (I), comprising the steps of:
(a) degreasing and/or sterilising a plastic substrate;
(b) immersing the plastic substrate in a solution containing said polymer in a concentration of from about 0.01 to about 5 g/100 ml;
(c) pulling out and drying the plastic substrate coated with said polymer on air or in an inert gas atmosphere. In step (a) of the process according to the present invention, the plastic substrate to be coated should be degreased in order to provide a good adhesion between the coating and surface of the plastic substrate.
In case the plastic articles are used for medicinal applications, the plastic article should be further sterilised. In this step (a) of the process of the present invention, it should be observed that the agents used for degreasing and/or sterilisation should not dissolve or attack the plastic substrate.
In step (b) the polymer, preferably poly[bis(trifluoroethoxy)polyphosphazene], is dissolved in a suitable solvent in a concentration of from about 0.01 to about 5 g/100 ml, preferably 0.01 to 3 g/100 ml. Examples of the solvent, but not limited to, include acetone, tetrahydrofuran, ethylacetate, methylethylketon, cyclohexanone, hexafluorobenzene and mixtures thereof. The immersion of the plastic substrate into the solution of said polymer can be carried out with any suitable means, for example semi-automatically or automatically, and does not exhibit any limitation.
The time period of immersion is dependent on the solvent or solvent mixture used and on the plastic substrate, i.e. the resin constituents, used, and may range from 1 second to several hours, during which the polymer molecules are deposited on the surface of the plastic substrate.
In step (c) the rate of the pulling or drawing out of the coated plastic substrates from the polymer solution is not specifically limited, but may depend on the plastic substrate used and its shape, and on pressure and temperature conditions such as standard pressure and room temperature. For instance, in case of hoses, the rate of pulling out is about 10 cm/min. Drying of the coated plastic substrates is carried out on air or in an inert gas atmosphere, such as argon or nitrogen. The drying can last from about 1 second to several hours, dependent on temperature, solvent, and plastic substrate used. A complete drying of the coated plastic substrates on air or in an inert gas atmosphere is preferred, in order to remove residual solvent, if present. Depending on the plastic substrate and solvent or solvent mixture used, the complete drying may require up to several days. It is also possible to remove the solvent or residual of solvents under vacuum.
In order to improve adhesion of the coating to the surface of the plastic substrate, an adhesion promoter as defined above can be applied to the surface of the plastic substrate prior to step (b) of the process of the present invention.
Moreover, it is also possible to subject the plastic substrate to a plasma treatment prior to step (b) of the process of the present invention in order to improve adhesion of the coating to the surface of the plastic substrate.
Moreover, a combination of firstly a plasma treatment and secondly the application of an adhesion promoter can be carried out prior to step (b) of the process of the present invention.
The coating of the adhesion promoter can be carried out with any method known in the prior art, such as solvent coating, vapour deposition etc.
In a preferred embodiment of the present invention, the plastic article can also be provided with a microstructure in the coating. The sizes of such microstructures do not exhibit any limitation, and can have sizes from a few nanometres up to several micrometers or even more. The microstructures can be applied by any method known in the art, such as photolithography or using electron radiation or ion radiation or using a laser. Microstructures of the coated plastic substrates can also be obtained by using direct ..writing" on the plastic substrates by means of a laser, electron radiation or X-ray. Alternatively, the microstructures can be obtained by so-called melt structuring, in which a thin wire is heated on the melting temperature of the polymer, said wire is melting the desired structure in the plastic substrate by direct contact. Particular advantages which are imparted by these structures can be achieved in that structures are engraved in the plastic substrates to be coated, which have a positive effect on the flow behaviour of liquids (e.g. shark skin or lotus effect).
A specific embodiment of the present invention is a wound coverage comprising at least one layer having a coating containing the above polymer (I), wherein said coating is in contact with the wound such as a burn wound, of a patient in need thereof. In this embodiment, the coating which is in contact with the wound of a patient, imparts excellent properties such as biobompatibility, anti-inflammatory effects etc. to the wound coverage, which is based on the polymer (I) used in the coating.
The wound coverage of the present invention can be built up as a two-layered structure, i.e. the plastic substrate and the coating, or three or more layered structure (..multi-layer structure"). In this context, it should be noted that the wound coverage of the present invention should be preferably gas(„air")-permeable, i.e. a porous wound coverage. This is achieved by providing e.g. a porous plastic substrate having pore sizes of from about a few nanometers, e.g. 5 nm, to about 30 μm, and a coating and optionally further layers which also exhibit pores comparable to the pores of the plastic substrate, for the gas-exchange. A specifically advantageous property of the wound coverage of the present invention is that the freshly formed cellular tissue or fibrous tissue originating from the wound, does not adhere or infiltrate the coating of said wound coverage.

Claims

Claims
1. A plastic article comprising a plastic substrate and a coating containing a polymer having the following general formula (I)
Figure imgf000011_0001
wherein n is from 2 to ∞ ,
R1 to R6 are the same or different and represent an alkoxy, alkylsulfonyl, dialkylamino or aryloxy group, or a heterocycloalkyl or heteroaryl group in which nitrogen is the heteroatom.
The plastic article according to claim 1 , wherein the coating has a thickness ranging from the polymer monolayer to about 20 μm.
The plastic article according to claim 2, wherein the coating has a thickness of up to 3 μm.
The plastic article according to anyone of claims 1 to 3, wherein a layer containing an adhesion promoter is provided between the surface of the plastic substrate and the coating.
The plastic article according to claim 4, wherein the adhesion promoter is amino-terminated.
6. The plastic article according to claim 5, wherein the adhesion promoter is aminopropylmethoxysilane.
7. The plastic article according to anyone of claims 1 to 6, wherein the plastic substrate is selected from the group consisting of polyethylene terephthalates, polyurethanes, polyethylenes, polyvinyl-chlorides and silicones and derivatives thereof.
8. A wound coverage comprising at least one layer having a coating containing a polymer
Figure imgf000012_0001
wherein n is from 2 to ∞ ,
R1 to R6 are the same or different and represent an alkoxy, alkylsulfonyl, dialkylamino or aryloxy group, or a heterocycloalkyl or heteroaryl group in which nitrogen is the heteroatom,
wherein said coating is in contact with the wound of a patient.
9. The wound coverage according to claim 8, having a multi-layer structure.
10. The wound coverage according to claim 8 or 9, further comprising a plastic substrate as a base material.
11. The wound coverage according to anyone of claims 8 to 10, which is gas- permeable.
12. A process for coating a plastic substrate using a polymer having the following general formula (I)
Figure imgf000013_0001
wherein n is from 2 to ∞ ,
R1 to R6 are the same or different and represent an alkoxy, alkylsulfonyl, dialkylamino or aryloxy group, or a heterocycloalkyl or heteroaryl group in which nitrogen is the heteroatom,
comprising the steps of:
(a) degreasing and/or sterilising the plastic substrate;
(b) immersing the plastic substrate in a solution containing said polymer in a concentration of from about 0.01 to about 5 g/100 ml;
(c) pulling out and drying the plastic substrate coated with said polymer on air or in an inert gas atmosphere.
13. The process according to claim 12, wherein prior to step (b) the plastic substrate is subjected to plasma treatment or is coated with an adhesion promoter, or is subjected to plasma treatment followed by coating the thus treated plastic substrate with an adhesion promoter.
PCT/EP2002/003268 2001-03-22 2002-03-22 Plastic articles having a polyphosphazene coating WO2002077073A2 (en)

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DE10113971.3 2001-03-22

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WO2009105761A3 (en) * 2008-02-22 2009-11-26 Celonova Biosciences, Inc. Multi-functional wound dressing matrices and related methods
WO2010036257A1 (en) * 2008-09-25 2010-04-01 Celonova Biosciences, Inc. Substrates containing polyphosphazene as matrices and substrates containing polyphosphazene with a micro-structured surface
US8007821B2 (en) 2001-01-11 2011-08-30 Celonova Biosciences Germany Gmbh Substrates containing polyphosphazene as matrices and substrates containing polyphosphazene with microstructured surface
US9080146B2 (en) 2001-01-11 2015-07-14 Celonova Biosciences, Inc. Substrates containing polyphosphazene as matrices and substrates containing polyphosphazene with a micro-structured surface

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US8007821B2 (en) 2001-01-11 2011-08-30 Celonova Biosciences Germany Gmbh Substrates containing polyphosphazene as matrices and substrates containing polyphosphazene with microstructured surface
US9080146B2 (en) 2001-01-11 2015-07-14 Celonova Biosciences, Inc. Substrates containing polyphosphazene as matrices and substrates containing polyphosphazene with a micro-structured surface
WO2008045953A3 (en) * 2006-10-10 2009-10-08 Celonova Biosciences, Inc. Compositions and devices comrising silicone and specific polyphosphazenes
WO2009105761A3 (en) * 2008-02-22 2009-11-26 Celonova Biosciences, Inc. Multi-functional wound dressing matrices and related methods
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WO2010036257A1 (en) * 2008-09-25 2010-04-01 Celonova Biosciences, Inc. Substrates containing polyphosphazene as matrices and substrates containing polyphosphazene with a micro-structured surface

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