Surface modification for coating

• US 9,289,540 B2
• Filed: 05/07/2010
• Issued: 03/22/2016
• Est. Priority Date: 05/08/2009
• Status: Active Grant

• Current Assignee: Greatbatch Limited (Greatbatch Incorporated)
• Original Assignee: Greatbatch Limited (Greatbatch Incorporated)
• Inventors: Ye, Qingshan
• Primary Examiner(s): Shosho, Callie
• Assistant Examiner(s): FREEMAN, JOHN D
• Application Number:
  US12/776,095
• Publication Number:
  US 20100286766A1
• Time in Patent Office: 2,146 Days
• US Class Current: 1/1
• CPC Class Codes: A61L 33/0017 using a surface active agent
• CPC Class Codes: B32B 2535/00 Medical equipment, e.g. bandage, prostheses or catheter
• CPC Class Codes: B32B 27/283 comprising polysiloxanes
• CPC Class Codes: B32B 27/285 comprising polyethers
• CPC Class Codes: B32B 27/34 comprising polyamides
• CPC Class Codes: B32B 27/365 comprising polycarbonates
• CPC Class Codes: B32B 27/40 comprising polyurethanes
• CPC Class Codes: Y10T 428/263 Coating layer not in excess of 5 mils thick or equivalent
• CPC Class Codes: Y10T 428/265 1 mil or less
• CPC Class Codes: Y10T 428/31507 Of polycarbonate
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31678 Of metal
• CPC Class Codes: Y10T 428/31725 Of polyamide

Abstract

A modified medical device substrate surface designed to improve adhesion of biomimetic surfactants to the medical device surface, thus reducing the risk of thrombosis is described. The surface modification is accomplished through either an application of a tie layer of a hydrophobic material on the substrate surface intermediate the biomimetic coating or through incorporation of a hydrophobic dopant in the polymeric substrate prior to extrusion or molding. Either method creates a hydrophobically modified surface that enhances the biomimetic surfactant bonding strength.

Claims

1. A substrate, which comprises:

a) a substrate composed of a material selected from the group consisting of silicone, polyether block amide (PEBA), polycarbonate and polyurethane, wherein the substrate has a surface;

b) a hydrophobic tie layer having opposed top and bottom tie layer surfaces and a surface contact angle greater than about 40°

, wherein the hydrophobic tie layer consists of a solvent and an unsaturated carboxylic acid amide at a concentration from about 0.1 to about 10 weight percent within the solvent; and

c) a biomimetic surfactant comprising an alkyl chain, wherein the hydrophobic tie layer is positioned between the substrate surface and the biomimetic surfactant; and

d) wherein the unsaturated carboxylic acid amide within the hydrophobic tie layer hydrophobically bonds to the alkyl chain of the biomimetic surfactant along the tie layer top surface and the unsaturated carboxylic acid amide hydrophobically bonds to the substrate surface along the tie layer bottom surface.

2. The substrate of claim 1 wherein the hydrophobic tie layer comprises erucamide.

3. The substrate of claim 1 wherein the biomimetic surfactant is selected from the group consisting of poly(N-vinyldextran aldonamide-co-N-vinylhexanamide), poly(N-vinyl dextran aldonamide-co-N-vinyl dodecanoamide)(PNVDA-co-PNVL), poly (N-vinyl hexyl amine-co-N-vinyl heparinamine)(PNVHA-co-PNVHep A), poly(N-vinyl hexyl amine-co-N-vinyl heparinamine-co-N-vinyl maltonoamide)(PNVHA-co-PN-VHepA-co-PNVM), and poly (N-vinyl-5-peptidyl-pentylamine-co-N-vinyl-dextranaldonamine-co-N-vinyl hexyl amine (PVAm(Pep:

Dex;

Hex)).

4. The substrate of claim 1 wherein the substrate surface is a surface selected from the group of medical devices consisting of a pacemaker, a defibrillator, a neurostimulator, an introducer, a lead, a catheter and a stent.

5. The substrate of claim 1 wherein a thickness of the hydrophobic tie layer is from about 0.1 nanometers to about 2.5 nanometers.

6. The substrate of claim 1 wherein a thickness of the hydrophobic tie layer is from about 2.5 nanometers to about 1 micrometer.

7. The substrate of claim 1 wherein a thickness of the hydrophobic tie layer is from about 1 micrometer to about 100 micrometers.

8. The substrate of claim 1 wherein the solvent is selected from the group consisting of tetrahydrofuran, dimethylsulfoxide, ethanol, methanol, ethylacetate, dimethylformamide, dimethylacetamide, dioxane, N-methyl pyrollidone, chloroform, hexane, heptanes, cyclohexane, toluene, formic acid, acetic acid, dichloromethane, and mixtures thereof.

9. A method for increasing the hydrophobicity of a substrate surface to enhance the adhesion of a biomimetic surfactant polymer to the substrate surface, the method comprising the steps of:

a) providing a substrate composed of a material selected from the group consisting of silicone, polyurethane, polyether block amide (PEBA), and polycarbonate, wherein the substrate has a substrate surface;

b) providing a biomimetic surfactant polymer comprising an alkyl chain;

c) providing a hydrophobic tie layer having opposed top and bottom hydrophobic tie layer surfaces, wherein the hydrophobic tie layer consisting of a solvent and an unsaturated carboxylic acid amide at a concentration ranging from about 0.1 to about 10 weight percent within the solvent;

d) applying the bottom hydrophobic tie layer surface to the substrate surface to thereby create a surface contact angle greater than about 40°

;

e) applying the biomimetic surfactant to the top polymer hydrophobic tie layer surface; and

f) wherein the unsaturated carboxylic acid amide within the hydrophobic tie layer hydrophobically bonds to the substrate surface along the bottom hydrophobic tie layer surface and the unsaturated carboxylic acid amide within the hydrophobic tie layer hydrophobically bonds to the alkyl chain of the biomimetic surfactant polymer along the top hydrophobic tie layer surface.

10. The method of claim 9 wherein the unsaturated carboxylic acid amide comprises erucamide.

11. The method of claim 9 wherein the solvent is selected from the group consisting of tetrahydrofuran, dimethylsulfoxide, ethanol, methanol, ethylacetate, dimethylformamide, dimethylacetamide, dioxane, N-methyl pyrollidone, chloroform, hexane, heptanes, cyclohexane, toluene, formic acid, acetic acid, dichloromethane, and mixtures thereof.

12. The method of claim 9 wherein the substrate surface is a surface selected from the group of medical devices consisting of a pacemaker, a defibrillator, a neurostimulator, an introducer, a lead, a catheter, and a stent.

13. The method of claim 9 wherein the biomimetic surfactant polymer is selected from the group consisting of poly(N-vinyl dextran aldonamide-co-N-vinyl hexanoamide), poly (N-vinyl dectran aldonamide)(PNVDA-co-PNVH), poly(N-vinyl dextran aldonamide-co-N-vinyl dodecanoamide)(PNVDA-co-PNVL), poly (N-vinyl hexyl amine-co-N-vinyl heparinamine)(PNVHA-co-PNVHep A), poly(N-vinyl hexyl amine-co-N-vinyl heparinamine-co-N-vinyl maltonoamide)(PNVHA-co-PN-VHepA-co-PNVM), and poly (N-vinyl-5-peptidyl-pentylamine-co-N-vinyl-dextranaldonamine-co-N-vinyl hexyl amine (PVAm(Pep:

Dex;

Hex)).

14. A substrate, which comprises:

a) a substrate composed of a material selected from the group consisting of silicone, polyether block amide (PEBA), polycarbonate and polyurethane, wherein the substrate has a surface;

b) a hydrophobic tie layer having opposed top and bottom tie layer surfaces and a contact angle greater than 40°

, wherein the tie layer consists of a tetrahydrofuran solvent and erucamide at a concentration ranging from about 0.1 to about 10 weight percent the solvent;

c) a biomimetic surfactant of poly(N-vinyl dextran aldonamide-co-N-vinyl hexanamide) comprising an alkyl chain, wherein the hydrophobic tie layer is positioned between the substrate surface and the biomimetic surfactant; and

d) wherein the erucamide within the hydrophobic tie layer hydrophobically bonds with the substrate surface along the bottom tie layer surface; and

e) wherein the erucamide within the hydrophobic tie layer hydrophobically bonds with the alkyl chain within the biomimetic surfactant along the top tie layer surface, thereby creating a hydrophobic bond therebetween the substrate surface and the biomimetic surfactant.

15. The substrate of claim 14 wherein the substrate surface is a surface selected from the group of medical devices comprising of a pacemaker, a defibrillator, a neurostimulator, an introducer, a lead, a catheter, and a stent.