COATED MEDICAL DEVICE

• US 20100114042A1
• Filed: 09/13/2007
• Published: 05/06/2010
• Est. Priority Date: 09/13/2006
• Status: Active Grant

• Current Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Original Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Inventors: Bruin, Peter, Dias, Aylvin Jorge Angelo Athanasius, Van Den Bosch, Edith Elisabeth M>, Rooijmans, Marnix, Van Benthem, Rudolfus Antonius Theodorus Maria
• Granted Patent: US 8,828,546 B2
• Time in Patent Office: Days
• US Class Current: 604/265
• CPC Class Codes: A61L 2420/02 Methods for coating medical devices
• CPC Class Codes: A61L 2420/06 Coatings containing a mixture of two or more compounds
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: A61L 29/10 Inorganic materials
• CPC Class Codes: A61L 29/14 Materials characterised by their function or physical properties , e.g. lubricating compositions
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: A61L 31/14 Materials characterised by their function or physical properties , e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• CPC Class Codes: C08G 2650/50 containing nitrogen, e.g. polyetheramines or Jeffamines(r)
• CPC Class Codes: C08G 65/3322 acyclic
• CPC Class Codes: C08G 65/33324 acyclic
• CPC Class Codes: C08L 33/26 Homopolymers or copolymers of acrylamide or methacrylamide
• CPC Class Codes: C09D 135/00 Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09D 135/02 Homopolymers or copolymers of esters C09D135/06, C09D135/08 take precedence
• CPC Class Codes: C09D 4/06 Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• CPC Class Codes: C09D 5/00 Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced electrically insulating plastics, resins or waxes H01B3/30; Filling pastes
• CPC Class Codes: C23C 14/06 characterised by the coating material C23C14/0021 , C23C14/04 take precedence
• CPC Class Codes: C23C 14/22 characterised by the process of coating
• CPC Class Codes: Y10T 428/1393 Multilayer [continuous layer]
• CPC Class Codes: Y10T 428/24975 No layer or component greater than 5 mils thick
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31562 : Next to polyamide [nylon, etc.]
• CPC Class Codes: Y10T 428/31725 : Of polyamide
• CPC Class Codes: Y10T 428/31935 : Ester, halide or nitrile of addition polymer

Abstract

The invention relates to an article comprising a coating, which coating comprises at least two layers, of which the inner layer is a primer layer, comprising a supporting network comprising a supporting polymer, and the outer layer is a functional layer comprising a multifunctional polymerizable compound.

Claims

1. Article, in particular a medical device, comprising a coating, which coating comprises at least two layers, of which the inner layer is a primer layer, comprising a supporting network comprising a supporting polymer, and the outer layer is a functional layer comprising

(A) at least one multifunctional polymerizable compound according to formula (1)

wherein G is a residue of a polyfunctional compound having at least n functional groups, wherein G is preferably hydrophilic, more preferably chosen from the group consisting of polyethers, polyurethanes, polyepoxides, polyamides, polyacrylamides, poly(meth)acrylics, polyoxazolidones, polyvinyl alcohols, polyethylene imines, polypeptides and polysaccharides, such as cellulose or starch or any combination of the above, and wherein G is more preferably a polymer comprising at least one polyethylene glycol or polypropylene glycol block;

wherein each R₁ and each R₂ independently represents hydrogen or a group selected from substituted and unsubstituted hydrocarbons which optionally contain one or more heteroatoms, preferably hydrogen or a C1-C20 hydrocarbon, more preferably hydrogen or a C1-C20 alkyl; and

wherein n is an integer having a value of at least 2, preferably 2-100, more preferably 2-8, in particular 2 or 3.

2. Article according to claim 1, wherein multifunctional polymerizable compound (A) has a number average molecular weight (Mn) of between 500 and 2000 g/mol.

3. Article according to claim 1, wherein the functional layer further comprises a functional polymer (C).

4. Article according to claim 1, wherein

the concentration of the supporting polymer (a) in the primer layer is in the range of 10 to 100 wt %, preferably 50 to 100 wt %, based on the total dry weight of the of the primer layer;

the concentration of the multifunctional polymerizable compound (A) according to formula (1) in the functional layer is in the range of 1-100%, preferably 5-90%, more preferably 8-60% based on the total dry weight of the functional layer;

the concentration of the functional polymer (C) in the functional layer is in the range of 0 to 99 wt %, preferably 20 to 95 wt % more preferably 40 to 95 wt %, based on the total dry weight of the functional layer.

5. Article according to claim 1, wherein the dry primer layer has a thickness of 0.1-20 μ

m, preferably 0.2-7 μ

m, more preferably 0.3-5 μ

m, even more preferably 0.5-3 μ

m and the dry functional layer has a thickness of at least 0.1 μ

m, wherein the total dry thickness of the coating is preferably 100 μ

m or less, in particular 50 μ

m or less, more in particular 35 μ

m or less, more preferably 15 μ

m or less.

6. Article according to claim 1 selected from the group consisting of catheters, endoscopes and laryngoscopes, tubes for feeding or drainage or endrotracheal use, guide wires, condoms, barrier coatings (e.g. for gloves, wound dressings, contact lenses, implants, extracorporeal blood conduits), membranes (e.g. for dialysis, blood filters, devices for circulatory assistance), packaging for foodstuff, razor blades, fishermen'"'"'s nets, conduits for wiring, water pipes having a coating inside, water slides, sports articles, cosmetic additives, mould release agents, and fishing lines and nets, preferably an article selected from the group consisting of catheters.

11. Primer coating formulation according to claim 1, comprising an organic solvent, preferably an alcohol, more preferably methanol and/or ethanol.

15. An article according to claim 1, wherein the functional polymer (C) is selected from the group consisting of poly(lactams), for example polyvinylpyrollidone (PVP), polyurethanes, homo- and copolymers of acrylic and methacrylic acid, polyvinyl alcohol, polyvinylethers, maleic anhydride based copolymers, polyesters, vinylamines, polyethylene imines, polyethyleneoxides, poly(carboxylic acids), polyamides, polyanhydrides, polyphosphazenes, cellulosics, for example methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, and hydroxypropylcellulose, heparin, dextran, polypeptides, for example collagens, fibrins, and elastin, polysaccharides, for example chitosan, hyaluronic acid, alginates, gelatin, and chitin, polyesters, for example polylactides, polyglycolides, and polycaprolactones, polypeptides, for example collagen, albumin, oligo peptides, polypeptides, short chain peptides, proteins, and oligonucleotides.

16. An article according to claim 1, wherein the weight average molecular weight of the functional polymer (C) is in the range of 20,000 to 10,000,000 g/mol, preferably 250,000 g/mol to 3,000,000 g/mol, more preferably 360,000 to 1,500 000 g/mol.

7. Primer coating formulation for providing an article with a primer layer comprising

(a) a supporting polymer selected from the group consisting of polyethers and polythioethers, including copolymers thereof, in a total concentration of 1-60 wt %, preferably 1-20 wt %, more preferably 2-10 wt %, most preferably 3-8 wt % based on the total weight of the formulation;

(b) a Norrish I type photo-initiator, preferably in a total concentration 1-10 wt %, more preferably 2-6 wt %, most preferably 3-5 wt % based on the weight of component (a); and

at least 68 wt %, preferably at least 75 wt %, more preferably at least 80 wt %, even more preferably at least 85 wt % of a solvent, wherein the components (a) and (b) are dissolved or dispersed.

8. Primer coating formulation according to claim 7, wherein the supporting polymer is selected from the group consisting of copolymers composed of at least (a-1) a polyether or polythioether;

(a-2) a moiety comprising at least two isocyanates; and

(a-3) a hydroxyalkylacrylate, a hydroxyalkylmethacrylate, a polyhydroxyalkylacrylate and a polyhydroxymethacrylate

9. Primer coating formulation or article according to claim 8, wherein (a-1) is selected from polyalkylene glycols (such as PEG and PPG and combinations thereof) and polytetrahydrofuran, preferably a poly(-methyl-1,4-butanediol)alt(tetramethyleneglycol);

(a-2) is selected from toluene diisocyanate and 4-cyclohexyldiisocyanate; and

(a-3) is selected from hydroxyethylacrylate and hydroxyethylmethacrylate.

10. Primer coating formulation or article according to claim 8, wherein the supporting polymer has a number average molecular weight in the range of 300-20,000, preferably 400-10,000, more preferably 500-5,000, even more preferably 750-3,000 g/mol.

14. Coating system for providing an article with a primer layer and a functional layer, comprising a primer coating formulation according to claim 7.

17. An assembly, comprising a primer coating formulation according to claim 7.

18. Method for preparing a coating comprising

applying a primer coating formulation according to claim 7 to a surface;

curing the supporting polymer;

applying a functional coating formulation; and

curing the functional coating formulation.

19. Medical coating obtainable by a method according to claim 18.

12. Functional coating formulation for coating an article with a functional layer comprising

(A) a multifunctional polymerizable compound according to formula (1) in a total concentration of 0.5-60 wt. %, in particular 0.5-30 wt %, preferably 0.5-20 wt %, more preferably 0.5-10 wt %, even more preferably 1-5 wt %, based on the total weight of the formulation;

(B) a photo-initiator, preferably in a total concentration of 0.1-10 wt. based on the total weight of (A) and (C);

(C) optionally a functional polymer in a total concentration of 0-60 wt %, based on the total weight of the formulation, in particular 0.5-30 wt %, preferably 0.5-20 wt %, more preferably 0.5-10 wt %, even more preferably 1-5 wt %; and

at least 68 wt %, preferably at least 75 wt %, more preferably at least 80 wt %, even more preferably at least 85 wt % of a solvent, wherein the components A), B), and optionally (C) are dissolved or dispersed.

13. Functional coating formulation according to claim 12, further comprising at least one surfactant (D), preferably in a concentration of 0.1-10 wt. based on the total weight of (A) and (C).

20. Hydrophilic coating obtainable by curing a functional coating formulation according to claim 12.

21. Lubricious coating obtainable by wetting a hydrophilic coating according to claim 20 applying a wetting fluid.

22. Use of a multifunctional polymerizable compound according to formula (1) in a medical, hydrophilic or lubricious coating.