WO2009103720A1 - Coating on metal - Google Patents

Coating on metal Download PDF

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Publication number
WO2009103720A1
WO2009103720A1 PCT/EP2009/051891 EP2009051891W WO2009103720A1 WO 2009103720 A1 WO2009103720 A1 WO 2009103720A1 EP 2009051891 W EP2009051891 W EP 2009051891W WO 2009103720 A1 WO2009103720 A1 WO 2009103720A1
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Prior art keywords
erl
union carbide
carbide corp
coating formulation
coating
Prior art date
Application number
PCT/EP2009/051891
Other languages
French (fr)
Inventor
Jacobus Loontjens
Original Assignee
Dsm Ip Assets B.V.
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.)
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Publication date
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Publication of WO2009103720A1 publication Critical patent/WO2009103720A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/34Macromolecular materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32Epoxy compounds containing three or more epoxy groups
    • C08G59/3236Heterocylic compounds
    • C08G59/3245Heterocylic compounds containing only nitrogen as a heteroatom
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50Amines
    • C08G59/5006Amines aliphatic
    • C08G59/5013Amines aliphatic containing more than seven carbon atoms, e.g. fatty amines
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606Coatings

Definitions

  • the invention relates to an anti-microbial coating formulation for coating a substrate comprising a metal.
  • Many medical devices such as hip and knee prosthesis, comprise metal components. Examples of metals used in medical devices include titanium. Such medical devices require a number of challenging properties. In particular, they need to be biocompatible and anti-microbial.
  • the problem to be solved is therefore to provide a coating that can be used on a metal, in particular titanium, and makes the medical device biocompatible and also provides antimicrobial properties.
  • a coating formulation suitable for coating metal substrates obtainable by a. Reacting a phosphoric acid or a derivative thereof with a polyepoxy compound, obtaining a reaction product comprising more than 10 mol% epoxy groups, b. Reacting the reaction product with an amine or a derivative thereof and optionally in the presence of a calcium phosphate salt.
  • Phosphoric acid, H 3 PO 4 , and its derivatives have a high affinity for metal substrates.
  • the metal surface can be oxidized first to improve adhesion even further.
  • H 3 P ⁇ 4 can form a bridge between the metal surface and the polyepoxy compound, yielding esters.
  • the first step in the reaction between H 3 PO 4 and the polyepoxy compound is depicted below:
  • the reaction product comprises more than 10 mol% epoxy groups, preferably more than 25 mol%, more preferably more than 50 mol% epoxy groups.
  • the reaction product can react with tertiairy amines to yield quaternary ammonium compounds, which have antibacterial properties, as depicted below.
  • R and R' independently represent a group selected from substituted and unsubstituted hydrocarbons which optionally contain one or more heteroatoms, preferably a C1-C20 hydrocarbon, more preferably a C1-C20 alkyl
  • X " represents -O 3 PO " , OH “ , CI “ , Br “ , I “ . -O 2 SO “ , -O 3 SO “ , NO 3 “ , or RCOO " .
  • polyepoxy compounds examples include diglycidyl ether of bisphenol A, ELO (epoxidized linseed oil) , ESO (epoxidized soybean oil), TGIC (triglycidyl isocyanaurate), diglycidyl ester of terephthalic acid, vinyl cyclohexane diepoxides, e. g. , 4-oxiranyl-cyclohexane (ERL-4206 from Union Carbide Corp. ) ; (3, 4-epoxycyclohexyl) methyl 3,4-epoxycyclohexanecarboxylate (ERL-4221 from Union Carbide Corp.
  • Examples of derivatives of phosphoric acid include phosphonic acids, phosphinic acid, and phosphorous acid (H 3 PO 3 ).
  • tertiary amines examples include tri(alkyl) amines, such as trimethyl amine, triethyl amine, and dimethyl dodecyl amine, and tri(aryl) amines.
  • a calcium phosphate salt is optional but may attribute to the biocompatibility of the coating, particularly to bone compatibility.
  • hydroxyapatite is used as the calcium phosphate salt.
  • the coating formulation may further comprise other components, such as hydrophilic polymers, additives or fillers.
  • additives may be present in a formulation respectively coating of the invention.
  • additives may in particular be selected from antioxidants, surfactants, UV-blockers, stabilisers such as anti-sagging agents, discolourants, lubricants, plasticizers, organic antimicrobial compounds, pigments, and dyes.
  • Such components may be selected from those known in the art, e.g. the prior art identified above. If present, the total concentration of such additives is usually less than 10 wt. % based on dry weight, in particular 5 wt. % or less.
  • Suitable antioxidants in particular include anti-oxidative vitamins (such as vitamin C and vitamin E) and phenolic antioxidants.
  • the surfactant may be an ionic (anionic/cationic), non-ionic or amphoteric surfactant.
  • ionic surfactants include alkyl sulphates (such as sodium dodecylsulphates), sodium cholate, bis(2-ethylhexyl)sulphosuccinate sodium salt, quaternary ammonium compounds, such as cetyltrimethylammonium bromide or chloride, lauryldimethylamine oxide, N-lauroylsarcosine sodium salt and sodium deoxycholate.
  • non-ionic surfactants include alkylpolyglucosides, branched secondary alcohol ethoxylates, octylphenol ethoxylates. If present, the surfactant concentration is usually 0.001-1 wt. %, preferably 0.05-0.5 wt. % of the liquid phase.
  • the formulation further comprises a carrier liquid in a sufficient amount to disperse or dissolve the other components of the formulation.
  • the carrier liquid concentration is usually at least 68 wt. %, preferably at least 75 wt. %, more preferably at least 80 wt. %, even more preferably at least 85 wt. % of the total weight of the composition.
  • the amount of solvent in the composition is preferably relatively high. For that reason the total solids content is preferably 20 wt. % or less.
  • the carrier liquid may be a single solvent or a mixture. It is chosen such that the components can be dissolved or at least dispersed therein. Preferably it - A -
  • water and/or an organic liquid soluble in water preferably an alcohol, more preferably a C1-C4 alcohol, in particular methanol and/or ethanol.
  • the invention further relates to a method for coating an article and to a coated article.
  • the formulation can be used to provide any article with an antimicrobial coating.
  • the formulation may be used to coat an article and the article is a medical device
  • the metal surface can be pre-treated in order to improve adherence of the antimicrobial coating, for instance a chemical and/or physical pre- treatment.
  • Suitable pre-treatments are known in the art for specific combinations of materials for the surface of the article. Examples of pre-treatments include plasma treatment, corona treatment, gamma irradiation, chemical washing, polarisation and oxidation.
  • formulation of the invention may be done in a manner per se.
  • curing is preferably carried out at elevated temperature, for example between 80 and 150 0 C or up to 200 0 C or up to 300 0 C as long as the mechanical properties or another property of the article and the coating are not adversely affected to an unacceptable extent.
  • Titanium test bars (5x5 cm) were coated with the aqueous solution of the polymer according to example 1 and heated in an oven at 100 0 C for 1 hour, yielding a coating of about 20 ⁇ m thick.
  • test samples Five of these test samples were evaluated in the JIS Z2801 antibacterial test. All the test samples were bacteria free. Samples were heated in boiling water for 7 days, and there was no sign of deterioration of the coating.

Abstract

The invention relates to a coating formulation suitable for coating metal substrates obtainable by a. Reacting a phosphoric acid or a derivative thereof with a polyepoxy compound, obtaining a reaction product comprising more than 10 mol% epoxy groups, b. Reacting the reaction product with an amine or a derivative thereof and optionally in the presence of a calcium phosphate salt.

Description

COATING ON METAL
The invention relates to an anti-microbial coating formulation for coating a substrate comprising a metal. Many medical devices, such as hip and knee prosthesis, comprise metal components. Examples of metals used in medical devices include titanium. Such medical devices require a number of challenging properties. In particular, they need to be biocompatible and anti-microbial. In order to make a metal-containing medical device biocompatible it can be coated with hydroxyapatite. However, to have a long lasting durability it is necessary to apply the hydroxyapatite in such a way that it is strongly and durably fixed in a coating composition, without deteriorating the biocompatibility of the system by the coating. Consequently, the coating should be acceptable for the body and compatible with hydroxyapatite. Coverage of titanium with a coating comprising hydroxyapatite will most likely result in a good biocompatibility, but this will obviously not result in antimicrobial properties.
The problem to be solved is therefore to provide a coating that can be used on a metal, in particular titanium, and makes the medical device biocompatible and also provides antimicrobial properties.
The above problem is solved according to the invention by providing a coating formulation suitable for coating metal substrates obtainable by a. Reacting a phosphoric acid or a derivative thereof with a polyepoxy compound, obtaining a reaction product comprising more than 10 mol% epoxy groups, b. Reacting the reaction product with an amine or a derivative thereof and optionally in the presence of a calcium phosphate salt.
Phosphoric acid, H3PO4, and its derivatives have a high affinity for metal substrates. Optionally, the metal surface can be oxidized first to improve adhesion even further.
H34 can form a bridge between the metal surface and the polyepoxy compound, yielding esters. The first step in the reaction between H3PO4 and the polyepoxy compound is depicted below:
Figure imgf000003_0001
The reaction product comprises more than 10 mol% epoxy groups, preferably more than 25 mol%, more preferably more than 50 mol% epoxy groups.
The reaction product can react with tertiairy amines to yield quaternary ammonium compounds, which have antibacterial properties, as depicted below.
Figure imgf000003_0002
wherein R and R' independently represent a group selected from substituted and unsubstituted hydrocarbons which optionally contain one or more heteroatoms, preferably a C1-C20 hydrocarbon, more preferably a C1-C20 alkyl, X" represents -O3PO", OH", CI", Br", I". -O2SO", -O3SO", NO3 ", or RCOO".
Examples of suitable polyepoxy compounds include diglycidyl ether of bisphenol A, ELO (epoxidized linseed oil) , ESO (epoxidized soybean oil), TGIC (triglycidyl isocyanaurate), diglycidyl ester of terephthalic acid, vinyl cyclohexane diepoxides, e. g. , 4-oxiranyl-cyclohexane (ERL-4206 from Union Carbide Corp. ) ; (3, 4-epoxycyclohexyl) methyl 3,4-epoxycyclohexanecarboxylate (ERL-4221 from Union Carbide Corp. ) ; bis [ (3, 4-epoxycyclohexyl) methyl] dicarboxylates, e. g. , the adipate (ERL-4229 from Union Carbide Corp. ), the succinate, and so forth; bis
[ (3, 4-epoxy-6- methylcyclohexyl) methyl] dicarboxylates, e. g. , the adipate (ERL-4289 from Union Carbide Corp. ), the pimelate, and so forth; bis (2,3-epoxycyclopentyl) ether (ERL-0400 from Union Carbide Corp. ); 2- (3, 4-epoxycyclohexyl) -5,5-spiro (2,3-epoxycyclohexane)-m-dioxane; 2- (3,4-epoxycyclohexyl)-5, 5-spiro (3,4-epoxy cyclohexane) -m-dioxane (ERL-4234 from Union Carbide Corp. ); (3,4-epoxy-6- methylcyclohexyl) methyl 3,4-epoxy-6-methylcyclohexane carboxylate (ERL-4201 from Union Carbide Corp. ); limonene dioxide (ERL-4269 from Union Carbide Corp.); dicyclopentadiene dioxide; and 1 , 2-bis (2,3-epoxycyclopentyl) ethane.
Examples of derivatives of phosphoric acid include phosphonic acids, phosphinic acid, and phosphorous acid (H3PO3).
Examples of tertiary amines include tri(alkyl) amines, such as trimethyl amine, triethyl amine, and dimethyl dodecyl amine, and tri(aryl) amines.
The use of a calcium phosphate salt is optional but may attribute to the biocompatibility of the coating, particularly to bone compatibility. Preferably hydroxyapatite is used as the calcium phosphate salt.
The coating formulation may further comprise other components, such as hydrophilic polymers, additives or fillers. Optionally one or more additives may be present in a formulation respectively coating of the invention. Such additives may in particular be selected from antioxidants, surfactants, UV-blockers, stabilisers such as anti-sagging agents, discolourants, lubricants, plasticizers, organic antimicrobial compounds, pigments, and dyes. Such components may be selected from those known in the art, e.g. the prior art identified above. If present, the total concentration of such additives is usually less than 10 wt. % based on dry weight, in particular 5 wt. % or less.
Suitable antioxidants in particular include anti-oxidative vitamins (such as vitamin C and vitamin E) and phenolic antioxidants.
The surfactant may be an ionic (anionic/cationic), non-ionic or amphoteric surfactant. Examples of ionic surfactants include alkyl sulphates (such as sodium dodecylsulphates), sodium cholate, bis(2-ethylhexyl)sulphosuccinate sodium salt, quaternary ammonium compounds, such as cetyltrimethylammonium bromide or chloride, lauryldimethylamine oxide, N-lauroylsarcosine sodium salt and sodium deoxycholate. Examples of non-ionic surfactants include alkylpolyglucosides, branched secondary alcohol ethoxylates, octylphenol ethoxylates. If present, the surfactant concentration is usually 0.001-1 wt. %, preferably 0.05-0.5 wt. % of the liquid phase.
The formulation further comprises a carrier liquid in a sufficient amount to disperse or dissolve the other components of the formulation. The carrier liquid concentration is usually at least 68 wt. %, preferably at least 75 wt. %, more preferably at least 80 wt. %, even more preferably at least 85 wt. % of the total weight of the composition. In view of handling properties (low viscosity) and/or in order to facilitate the application of the composition such that a coating with the desired thickness is obtained, the amount of solvent in the composition is preferably relatively high. For that reason the total solids content is preferably 20 wt. % or less.
The carrier liquid may be a single solvent or a mixture. It is chosen such that the components can be dissolved or at least dispersed therein. Preferably it - A -
comprises water and/or an organic liquid soluble in water, preferably an alcohol, more preferably a C1-C4 alcohol, in particular methanol and/or ethanol.
As described above, the invention further relates to a method for coating an article and to a coated article. In principle, the formulation can be used to provide any article with an antimicrobial coating. In particular, the formulation may be used to coat an article and the article is a medical device
If desired, the metal surface can be pre-treated in order to improve adherence of the antimicrobial coating, for instance a chemical and/or physical pre- treatment. Suitable pre-treatments are known in the art for specific combinations of materials for the surface of the article. Examples of pre-treatments include plasma treatment, corona treatment, gamma irradiation, chemical washing, polarisation and oxidation.
Application of the formulation of the invention may be done in a manner per se. In general, curing is preferably carried out at elevated temperature, for example between 80 and 150 0C or up to 200 0C or up to 300 0C as long as the mechanical properties or another property of the article and the coating are not adversely affected to an unacceptable extent.
The invention will now be illustrated by the following examples.
EXAMPLES
Example 1
To 9.8 g (0.1 mol) H3PO4 dissolved in 100 ml water in a glass flask of 500 ml were added 34 g (0.1 mol) di-glycidyl ether of bisphenol A, 2.97 g (0.01 mol) triglycidyl isocyanurate (TGIC), 21.3 g (0.01 mol) dimethyl dodecyl amine and 10 g hydroxyapatite. The mixture was stirred for 20 minutes at room temperature, resulting in a viscous solution.
Example 2
To 2,0 g (0.02 mol) H3PO4 dissolved in 100 ml water in a glass flask of 500 ml were added 34 g (0.1 mol) di-glycidyl ether of bisphenol A, 2.97 g (0.01 mol) triglycidyl isocyanurate (TGIC), 21.3 g (0.01 mol) dimethyl dodecyl amine and 10 g hydroxyapatite. The mixture was stirred for 20 minutes at room temperature, resulting in a viscous solution. Example 3
A titanium metal plate was cleaned thoroughly with an aqueous HCI solution and rinsed with demineralized water until no chlorine could be detected any more in the rinsing water. Titanium test bars (5x5 cm) were coated with the aqueous solution of the polymer according to example 1 and heated in an oven at 100 0C for 1 hour, yielding a coating of about 20 μm thick.
Five of these test samples were evaluated in the JIS Z2801 antibacterial test. All the test samples were bacteria free. Samples were heated in boiling water for 7 days, and there was no sign of deterioration of the coating.

Claims

1. Coating formulation suitable for coating metal substrates obtainable by a. Reacting a phosphoric acid or a derivative thereof with a polyepoxy compound, obtaining a reaction product comprising more than 10 mol% epoxy groups, b. Reacting the reaction product with an amine or a derivative thereof and optionally in the presence a calcium phosphate salt.
2. Coating formulation according to claim 1 , wherein the polyepoxy compound is chosen from the group consisting of diglycidyl ether of bisphenol A, ELO
(epoxidized linseed oil) , ESO (epoxidized soybean oil), TGIC (triglycidyl isocyanaurate), diglycidyl ester of terephthalic acid, vinyl cyclohexane diepoxides, e. g., 4-oxiranyl-cyclohexane (ERL-4206 from Union Carbide Corp.); (3, 4-epoxycyclohexyl) methyl 3,4-epoxycyclohexanecarboxylate (ERL- 4221 from Union Carbide Corp. ); bis [ (3, 4-epoxycyclohexyl) methyl] dicarboxylates, e. g., the adipate (ERL-4229 from Union Carbide Corp. ), the succinate, and so forth; bis [ (3, 4-epoxy-6- methylcyclohexyl) methyl] dicarboxylates, e. g., the adipate (ERL-4289 from Union Carbide Corp. ), the pimelate, and so forth; bis (2,3-epoxycyclopentyl) ether (ERL-0400 from Union Carbide Corp. ); 2- (3, 4-epoxycyclohexyl) -5,5-spiro (2,3-epoxycyclohexane)- m-dioxane; 2- (3,4-epoxycyclohexyl)-5, 5-spiro (3,4-epoxy cyclohexane) -m- dioxane (ERL-4234 from Union Carbide Corp.); (3,4-epoxy-6- methylcyclohexyl) methyl 3,4-epoxy-6-methylcyclohexane carboxylate (ERL- 4201 from Union Carbide Corp. ); limonene dioxide (ERL-4269 from Union Carbide Corp. ); dicyclopentadiene dioxide; and 1 , 2-bis (2,3- epoxycyclopentyl) ethane.
3. Coating formulation according to claim 1 or 2, wherein the amine is a tertiary amine.
4. Coating formulation according to anyone of claims 1-3, wherein the phosphate salt is hydroxyapatite.
5. Coating formulation accoding to anyone of claims 1-4, wherein the metal substrate is a titanium substrate.
6. Medical device coated with the coating formulation according to any one of claims 1-5.
7. Use of the coating formulation according to any one of claims 1-5 in medical applications.
PCT/EP2009/051891 2008-02-18 2009-02-18 Coating on metal WO2009103720A1 (en)

Applications Claiming Priority (2)

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EP08151577.7 2008-02-18
EP08151577 2008-02-18

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB952842A (en) * 1959-07-22 1964-03-18 Unisearch Ltd Epoxy resin compositions, and articles formed therewith adapted for surgical use
US4397970A (en) * 1981-06-24 1983-08-09 The Dow Chemical Company Process for epoxy phosphate coating resins
US4461857A (en) * 1982-09-29 1984-07-24 Desoto, Inc. Thermosetting aqueous coating compositions containing epoxy-phosphate dispersions
EP0212193A2 (en) * 1985-08-09 1987-03-04 Michael Montgomery Walker Prosthesis with bone fixation
WO1994015652A1 (en) * 1993-01-15 1994-07-21 University Of Southampton Load bearing implantable prosthesis
DE19755334A1 (en) * 1997-12-15 1999-06-24 Wilhelm Dr Aicher Coating material for prostheses and prosthesis part coated with them

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB952842A (en) * 1959-07-22 1964-03-18 Unisearch Ltd Epoxy resin compositions, and articles formed therewith adapted for surgical use
US4397970A (en) * 1981-06-24 1983-08-09 The Dow Chemical Company Process for epoxy phosphate coating resins
US4461857A (en) * 1982-09-29 1984-07-24 Desoto, Inc. Thermosetting aqueous coating compositions containing epoxy-phosphate dispersions
EP0212193A2 (en) * 1985-08-09 1987-03-04 Michael Montgomery Walker Prosthesis with bone fixation
WO1994015652A1 (en) * 1993-01-15 1994-07-21 University Of Southampton Load bearing implantable prosthesis
DE19755334A1 (en) * 1997-12-15 1999-06-24 Wilhelm Dr Aicher Coating material for prostheses and prosthesis part coated with them

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