EP2285858A1

EP2285858A1 - Hydrophilic polyurethane coatings

Info

Publication number: EP2285858A1
Application number: EP09753633A
Authority: EP
Inventors: Jürgen Köcher
Original assignee: Bayer MaterialScience AG
Current assignee: Covestro Deutschland AG
Priority date: 2008-05-28
Filing date: 2009-05-19
Publication date: 2011-02-23
Also published as: CN102046685B; WO2009143978A1; CN102046685A; JP2011523962A; JP5437364B2; US20110077310A1; DE102008025614A1; HK1157368A1

Abstract

The invention relates to the use of specific polyurethane urea coatings, the polyurethane urea being terminated by a copolymer unit which is constituted of polyethylene oxide and polypropylene oxide.

Description

Hydrophilic polyurethane coatings

The present invention relates to the use of a coating composition in the form of a polyurethane dispersion for the production of hydrophilic coatings, in particular the use of the coating composition for coating devices, in particular medical devices. In addition, the hydrophilic coating materials according to the invention are also applicable to the protection of surfaces from fogging, for the production of easy-to-clean or self-cleaning surfaces and to reduce the dirt absorption of these surfaces. The hydrophilic coating materials of the invention are also capable of reducing or avoiding the formation of water spots on surfaces.

Furthermore, hydrophilic surfaces can be produced with the polyurethane solutions according to the invention, which are no longer grown to a significant extent by organisms living in the water (antifouling properties). Further fields of application of these coating materials according to the invention are applications in the printing industry, for cosmetic formulations as well as for systems also outside of medical technology applications which release active ingredients.

The use of medical devices, such as catheters, can be greatly improved by the equipment with hydrophilic surfaces. The insertion and displacement of urine or blood vessel catheters is made easier by the fact that hydrophilic surfaces in contact with blood or urine adsorb a water film. As a result, the friction of the catheter surface is reduced compared to the vessel walls, so that the catheter is easier to use and move. Also, a direct washing of the equipment before the intervention can be made to reduce the friction by forming a homogeneous Wasserfϊlms. Affected patients have less pain and the risk of injury to the vessel walls is thereby reduced. In addition, the use of catheters always involves the risk of blood clots forming. In this context, hydrophilic coatings are generally considered helpful for antithrombogenic coatings.

Polyurethane coatings, which are prepared starting from solutions or dispersions of corresponding polyurethanes, are fundamentally suitable for the production of corresponding surfaces.

Thus, US Pat. No. 5,589,563 describes the use of surface-modified end-group coatings for polymers used in the field of biomedicine, which can also be used for coating medical devices. The resulting coatings are prepared from solutions or dispersions and the polymeric coatings comprise various end groups selected from amines, fluorinated alkanols, polydimethylsiloxanes and amine-terminated polyethylene oxides. However, these polymers have a coating for medical devices no satisfactory properties, especially with regard to the required hydrophilicity on.

A disadvantage of aqueous dispersions, as described, inter alia, in US Pat. No. 5,589,563, is, moreover, that the size of the dispersed particles makes the coatings relatively rough. In addition, the resulting coatings of aqueous dispersions are generally not sufficiently stable. Therefore, there is a need for hydrophilic coating systems which have excellent hydrophilicity and at the same time a relatively smooth surface and high stability. Polyurethane solutions per se are known from the prior art, but have not been used for coating medical devices, with the exception of the already mentioned polyurethane solutions according to US Pat. No. 5,589,563.

For example, DE-A 22 21 798 describes a process for the preparation of stable and light-stable solutions of polyurethane ureas from prepolymers having terminal isocyanate groups and diamines in low-polar solvents, where prepolymers of a) substantially linear polyhydroxyl compounds having molecular weights of about 500 to 5000, b) optionally low molecular weight dihydroxy compounds and c) aliphatic or cycloaliphatic diisocyanates, wherein the molar ratio of hydroxyl and isocyanate groups between about 1: 1.5 and 1: 5, in a solvent (mixture) of optionally chlorinated aromatic and / or chlorinated aliphatic hydrocarbons and primary, secondary and / or tertiary aliphatic and / or cycloaliphatic alcohols with diamines as Kettenver longer be reacted, wherein at least 80 mol% of the chain extender 1,4-diamino-cyclohexane with a cis / trans isomer ratio between 10/90 and nd 60/40. These polyurethaneurea solutions are used to produce lightfast films and coatings.

Furthermore, DE-A 22 52 280 describes a process for coating textile substrates by the reversal process with adhesive and topcoats from solutions of aliphatic, segmented polyurethane elastomers which are polycarbonate-containing.

Furthermore, EP-A 0 125 466 describes a process for the multi-coat reverse coating of textile, preferably sheet-like, bases for the production of synthetic leather from at least one top coat solution and at least one adhesion coat solution based on polyurethanes. None of these documents describes a hydrophilic polyurethane resin solution which is used for coating purposes of medical devices and meets the previously defined requirements.

It is an object of the present invention to provide compositions which are suitable for the coating of medical devices having hydrophilic surfaces. Since these surfaces are often used in blood contact, the surfaces of these materials should also have good blood compatibility and in particular reduce the risk of the formation of blood clots. Furthermore, the resulting coatings should be smooth and have high stability.

The subject of this invention are coating compositions in the form of specific polyurethane solutions.

The polyurethane solutions to be used according to the invention comprise at least one polyurethaneurea which is terminated with a copolymer unit of polyethylene oxide and polypropylene oxide.

According to the invention, it has been found that compositions of these particular polyurethaneureas in solutions are eminently suitable for the production of coatings on medical devices, provide them with an outstanding hydrophilic coating, form smooth surfaces, have high stability and at the same time the risk of formation of blood clots during treatment reduce with the medical device.

Polyurethane ureas in the context of the present invention are polymeric compounds which

(a) at least two repeating units containing urethane groups of the following general structure

O

- N- u- O- H and

(b) at least one repeating unit containing urea groups

exhibit.

The coating compositions in the form of a solution to be used according to the invention are based on polyurethane adhesives which have essentially no ionic have modification. For the purposes of the present invention, this is understood to mean that the polyurethaneureas to be used according to the invention have essentially no ionic groups, in particular no sulfonate, carboxylate, phosphate and phosphonate groups. In the context of the present invention, the term "essentially no ionic groups" is understood to mean that the resulting coating of the polyurethaneurea has ionic groups with a proportion of generally not more than 2.50% by weight, in particular not more than 2.00% by weight. , preferably at most 1.50 wt .-%, particularly preferably at most 1.00 wt .-%, especially at most 0.50 wt .-%, more especially no ionic groups.Thus, it is particularly preferred that the polyurethaneurea no ionic groups Since the high concentration of ions in organic solution means that the polymer is no longer sufficiently soluble and thus stable solutions can not be obtained, if the polyurethane used according to the invention has ionic groups, these are preferably carboxylates.

The coating compositions in the form of solutions used in the invention include polyurethanes, which are preferably substantially linear molecules but may also be branched. In the context of the present invention, "substantially linear molecules" are readily cross-linked systems which contain a polyol component having an average hydroxyl functionality of preferably 1.7 to 2.3, in particular 1.8 to 2.2, particularly preferably 1.9 to 2.1.

The number-average molecular weight of the polyurethane ureas preferably used according to the invention is preferably from 1000 to 200,000, more preferably from 5,000 to 100,000. The number-average molecular weight is measured as the standard in dimethylacetamide at 30 ° C. against polystyrene.

polyurethane ureas

The coating systems based on polyurethane ureas to be used according to the invention are described in more detail below. The polyurethane-containing coating compositions according to the invention in the form of a solution are prepared by reacting synthesis components which comprise at least one polycarbonate polyol component, at least one polyisocyanate component, at least one polyoxyalkylene ether component, at least one diamine and / or aminoalcohol component and optionally one further polyol component.

In the following, the individual components are described in more detail. (a) polycarbonate polyol

The polyurethaneurea-based coating composition of the invention in the form of a solution has units derived from at least one hydroxyl-containing polycarbonate. Basically suitable for introducing units based on a hydroxyl-containing polycarbonate are polyhydroxy compounds having an average hydroxyl functionality of 1.7 to 2.3, preferably from 1.8 to 2.2, particularly preferably from 1.9 to 2.1.

As hydroxyl-containing polycarbonates are polycarbonates of OHZahl specific molecular weight of preferably 400 to 6000 g / mol, more preferably 500 to 5000 g / mol, in particular from 600 to 3000 g / mol in question, for example, by reaction of carbonic acid derivatives, such as diphenyl carbonate, Dimethyl carbonate or phosgene, with polyols, preferably diols, are available. Examples of such diols are ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane , 2-methyl-l, 3-propanediol, 2,2,4-trimethylpentane-l, 3-diol, di-, tri- or tetraethylene glycol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromobisphenol A but also lactone-modified diols in question.

Preferably, the diol component contains from 40 to 100% by weight of hexanediol, preferably 1,6-hexanediol and / or hexanediol derivatives, preferably those which have, in addition to terminal OH groups, ether or ester groups, e.g. Products obtained by reacting 1 mole of hexanediol with at least 1 mole, preferably 1 to 2 moles of caprolactone or by etherification of hexanediol with itself to di- or Trihexylenglykol. Polyether-polycarbonate diols can also be used. The hydroxyl polycarbonates should be substantially linear. However, they may optionally be easily branched by the incorporation of polyfunctional components, in particular low molecular weight polyols. Glycerol, trimethylolpropane, hexanetriol-1,2,6, butanetriol-1,2,4, trimethylolpropane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside or 1,3,4,6-dianhydrohexitols are suitable for this purpose, for example. Preference is given to such polycarbonates based on 1,6-hexanediol, as well as modifying co-diols such. B. 1,4-butanediol or ε-caprolactone. Further preferred polycarbonate diols are those based on mixtures of 1,6-hexanediol and 1,4-butanediol.

The polycarbonate is preferably formed substantially linear and has only a slight three-dimensional cross-linking, so that polyurethanes are formed, which have the aforementioned specification. (b) polyisocyanate

The polyurethaneurea-based coating composition according to the invention has units which are based on at least one polyisocyanate as the synthesis component. As polyisocyanates (b) it is possible to use all aromatic, araliphatic, aliphatic and cycloaliphatic isocyanates known to those skilled in the art having an average NCO functionality> 1, preferably> 2, individually or in any mixtures with one another, it being immaterial whether these are or phosgene-free processes. These may also have iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, acylurea and / or carbodiimide structures. The polyisocyanates can be used individually or in any mixtures with one another.

Isocyanates from the series of aliphatic or cycloaliphatic representatives are preferably used, these having a carbon skeleton (without the NCO groups contained) of 3 to 30, preferably 4 to 20 carbon atoms.

Particularly preferred compounds of component (b) correspond to the abovementioned type with aliphatically and / or cycloaliphatically bonded NCO groups such as, for example, bis (isocyanatoalkyl) ether, bis- and tris (isocyanatoalkyl) benzenes, - toluene, and also -xylols, propane diisocyanates , Butane diisocyanates, pentane diisocyanates, hexane diisocyanates (eg hexamethylene diisocyanate, HDI), heptane diisocyanates, octane diisocyanates, nonane diisocyanates (eg trimethyl-HDI (TMDI) generally as a mixture of 2,4,4- and 2,2,4-isomers ), Nonanetriisocyanates (eg 4-isocyanatomethyl-l, 8-octanediisocyanate), decane diisocyanates, decane triisocyanates, undecane diisocyanates, undecane triisocyanates, dodecane diisocyanates, dodecane triisocyanates, 1,3- and 1,4-bis- (isocyanato-methyl) cyclohexanes ( H ₆ XDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate, IPDI), bis (4-isocyanatocyclohexyl) methane (Hi ₂ MDI) or bis (isocyanatomethyl) norbornane (NBDI).

Very particularly preferred compounds of component (b) are hexamethylene diisocyanate (HDI), trimethyl-HDI (TMDI), 2-methylpentane-l, 5-diisocyanate (MPDI), isophorone diisocyanate (EPDI), 1,3- and 1,4 Bis (isocyanatomethyl) cyclohexane (H ₆ XDI), bis (isocyanatomethyl) norbornane (NBDI), 3 (4) isocyanatomethyl-1-methylcyclohexyl isocyanate (IMCI) and / or 4,4'-bis (isocyanatocyclohexyl ) methane (H ₁₂ MDI) or mixtures of these isocyanates. Further examples are derivatives of the above diisocyanates with uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure having more than two NCO groups.

The amount of component (b) in the coating composition to be used in the present invention is preferably 1.0 to 3.5 mol, more preferably 1.0 to 3.3 mol, in particular 1.0 to 3.0 mol, in each case based on the component (a) of the coating composition to be used according to the invention.

(c) Polyoxyalkylene ethers The polyurethaneurea used in the present invention has units derived from a copolymer of polyethylene oxide and polypropylene oxide as the constitutional component. These copolymer units are present as end groups in the polyurethaneurea and cause a hydrophilization of the coating composition according to the invention. Nonionically hydrophilicizing compounds (c) are, for example, monovalent polyalkylene oxide polyether alcohols having a statistical average of 5 to 70, preferably 7 to 55, ethylene oxide units per molecule, as are obtainable in a conventional manner by alkoxylation of suitable starter molecules (eg in Ullmanns Enzyklopadie der technischen Chemie 4th Edition, Volume 19, Verlag Chemie, Weinheim pp. 31-38). Examples of suitable starter molecules are saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomers pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n Hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers, such as, for example, diethylene glycol monobutyl ether, unsaturated alcohols, such as allyl alcohol, 1,1-dimethylallyl alcohol or oleic alcohol, aromatic alcohols such as phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols such as benzyl alcohol, anisalcohol or cinnamyl alcohol, secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, bis (2-ethylhexyl) amine, N-methyl - and N-ethylcyclohexylamine or dicyclohexylamine and heterocyclic secondary amines such as morpholine, pyrrolidine, piperide in or 1H-pyrazole. Preferred starter molecules are saturated monoalcohols. Diethylene glycol monobutyl ether is particularly preferably used as starter molecule.

The alkylene oxides ethylene oxide and propylene oxide can be used in any order or even as a mixture in the alkoxylation reaction.

The polyalkylene oxide polyether alcohols are mixed polyalkylene oxide polyethers of ethylene oxide and propylene oxide, the alkylene oxide units of which preferably consist of at least 30 mol%, particularly preferably at least 40 mol%, of ethylene oxide units. Preferred nonionic compounds are monofunctional mixed polyalkylene oxide polyethers which have at least 40 mol% of ethylene oxide and not more than 60 mol% of propylene oxide units. The average molecular weight of the polyoxyalkylene ether is preferably 500 g / mol to 5000 g / mol, particularly preferably 1000 g / mol to 4000 g / mol, in particular 1000 to 3000 g / mol.

The amount of component (c) in the coating composition to be used according to the invention is preferably from 0.01 to 0.5 mol, particularly preferably from 0.02 to 0.4 mol, in particular from 0.04 to 0.3 mol, in each case based on the component (a) of the coating composition to be used according to the invention.

According to the invention, it has been possible to show that the polyurethaneureas having terminal groups based on mixed polyoxyalkylene ethers of polyethylene oxide and polypropylene oxide are particularly suitable for producing coatings having a high hydrophilicity. As shown below in comparison to polyurethane ureas which are terminated only by polyethylene oxide, the coatings according to the invention have a markedly low contact angle and are therefore more hydrophilic.

(d) diamine or aminoalcohol

The polyurethaneurea solution according to the invention has units which are based on at least one diamine or an amino alcohol as the synthesis component and serve as so-called chain extenders (d). Such chain extenders include di- or polyamines and hydrazides, for example hydrazine, ethylenediamine, 1,2- and 1,3-diaminopropane, 1, 4-diaminobutane, 1,6-diaminohexane, isophoronediamine, isomer mixture of 2,2,4- and 2,4,4-trimethyl-hexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 1,3- and 1,4-xylylenediamine, α, α, α ', α'-tetramethyl-l, 3- and 1,4-xylylenediamine and 4,4'-diamino-dicyclohexylmethane, dimethylethylenediamine, hydrazine, adipic dihydrazide, 1,4-bis- (aminomethyl) -cyclohexane, 4,4'-diamino-3,3'-dimethyl-dicyclohexylmethane and other (C 1 -C ₄ ) -oi. and tetraalkyldicyclohexylmethanes, e.g. 4,4'-diamino-3,5-diethyl-3 ', 5'-diisopropyldicyclohexylmethane.

As diamines or amino alcohols are generally suitable low molecular weight diamines or amino alcohols containing active hydrogen with respect to NCO groups of different reactivity, such as compounds containing not only a primary amino group but also secondary amino groups or in addition to an amino group (primary or secondary) and OH groups exhibit. Examples of these are primary and secondary amines, such as 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, furthermore amino alcohols, such as N-aminoethylethanolamine, ethanolamine , 3-aminopropanol, neopentanolamine and more preferably diethanolamine. The component (d) of the coating composition to be used according to the invention can be used as a chain extender in their preparation.

The amount of constituent (d) in the solution according to the invention of the coating composition is preferably 0.1 to 1.5 mol, more preferably 0.2 to 1.3 mol, in particular 0.3 to 1.2 mol, in each case based on the component (a) of the coating composition to be used according to the invention.

(e) polyols

In a further embodiment, the coating composition according to the invention which is in the form of a solution comprises additional units which are based on at least one further polyol as the synthesis component.

The other low molecular weight polyols (e) used to build up the polyurethane ureas generally cause stiffening and / or branching of the polymer chain. The molecular weight is preferably 62 to 500 g / mol, particularly preferably 62 to 400 g / mol, in particular 62 to 200 g / mol.

Suitable polyols may contain aliphatic, alicyclic or aromatic groups. Mentioned here are, for example, the low molecular weight polyols having up to about 20 carbon atoms per molecule, such as. B. Ethyenglykol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1, 4-butanediol, 1,3-butylene glycol, cyclohexanediol, 1, 4-cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, Hydroquinone dihydroxyethyl ether, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), and trimethylolpropane, glycerol or pentaerythritol and mixtures thereof and optionally also further low molecular weight polyols. Also, ester diols such as e.g. α-Hydroxybutyl-ε-hydroxy-caproic acid esters, ω-hydroxyhexyl-γ-hydroxybutyric acid esters, adipic acid (β-hydroxyethyl) esters or terephthalic acid bis (β-hydroxyethyl) esters may be used.

The amount of component (e) in the coating composition to be used in the present invention is preferably 0.05 to 1.0 mol, more preferably 0.05 to 0.5 mol, especially 0.1 to 0.5 mol, in each case based on the constituent (a) the coating composition to be used in the invention.

(f) Further amine- and / or hydroxy-containing building blocks (structural component)

The reaction of the isocyanate-containing component (b) with the hydroxy- or amine-functional compounds (a), (c), (d) and optionally (e) is usually carried out while maintaining a slight excess of NCO over the reactive hydroxy or amine compounds. At the end point of the reaction by reaching a target viscosity remains of active isocyanate remain. These residues must be blocked so that it does not react with large polymer chains. Such a reaction leads to the three-dimensional networking and gelling of the approach. The processing of such a coating solution is no longer possible. Usually, the approaches contain high levels of alcohols. These alcohols block the remaining isocyanate groups within several hours of standing or stirring the mixture at room temperature.

However, if it is desired to block the remaining residual isocyanate content rapidly, the polyurethaneurea coating compositions provided according to the invention in the form of a solution can also contain monomers (f) as structural components, which are located at the chain ends and close them.

These structural components are derived, on the one hand, from monofunctional compounds reactive with NCO groups, such as monoamines, in particular mono-secondary amines or monoalcohols. Examples include ethanol, n-butanol, ethylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadecan-ol, methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, Dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine and suitable substituted derivatives thereof.

Since the building blocks (f) are essentially used in the coating composition of the invention in the form of a solution to destroy the NCO excess, the required amount depends essentially on the amount of NCO excess and can not be specified in general ,

Preferably, these components are omitted during the synthesis. Unreacted isocyanate is preferably converted into terminal urethanes by the solvent alcohols present in very large concentrations.

(g) other ingredients

The inventively provided solutions of the polyurethaneurea coating composition may moreover contain further constituents and additives customary for the intended purpose. An example of this are pharmacologically active substances, pharmaceuticals and additives which promote the release of pharmacologically active substances ("drug-eluting additives").

Pharmacological active ingredients or medicaments which can be used in the coatings according to the invention on the medical devices and can therefore be contained in the solutions according to the invention are, for example, thrombore-resistant agents, antibiotic agents, antitumor agents, growth hormones, antiviral agents, antiangiogenic agents, angiogenic agents Means, antimitotic, anti-inflammatory de means, cell cycle regulating agents, genetic agents, hormones, and their homologues, derivatives, fragments, pharmaceutical salts and combinations thereof.

Specific examples of such pharmacologically active agents or drugs therefore include thromboresistant (non-thrombogenic) agents or other agents for suppressing acute thrombosis, stenosis or late re-stenosis of the arteries, for example heparin, streptokinase, urokinase, tissue plasminogen activator, Anti-thromboxane B ₂ agents; Anti-B-thromboglobulin, prostaglandin-E, aspirin, dipyridol, anti-thromboxane A ₂ agents, murine monoclonal antibody 7E3, triazolopyrimidine, ciprosten, hirudin, ticlopidine, nicorandil, etc. A growth factor may also be considered as a Medicaments can be used to suppress intimal fibromuscular hyperplasia at the arterial stenosis site, or any other inhibitor of cell growth at the stenosis site can be used.

The pharmacological agent or drug may also consist of a vasodilator to counteract vasospasm, for example an antispasmodic agent such as papaverine. The drug may be a vasoactive agent per se, such as calcium antagonists, or α- and β-adrenergic agonists or antagonists. In addition, the therapeutic agent may be a biological adhesive such as medical grade cyanoacrylate or fibrin used, for example, for adhering a tissue valve to the wall of a coronary artery. The therapeutic agent may also be an antineoplastic agent such as 5-fluorouracil, preferably with a controlling releasing carrier for the agent (e.g., for the application of a sustained controlled release anti-neoplastic agent at a tumor site).

The therapeutic agent may be an antibiotic, preferably in combination with a sustained release, controlling releasing carrier, from the coating of a medical device to a localized source of infection within the body. Similarly, the therapeutic agent may contain steroids for the purpose of suppressing inflammation in localized tissue or for other reasons. Specific examples of suitable drugs include:

(a) heparin, heparin sulfate, hirudin, hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate, lyric agents including urokinase and streptokinase, their homologues, analogues, fragments, derivatives and pharmaceutical salts thereof; (b) antibiotic agents such as penicillins, cephalosprins, vacomycins, aminoglycosides, quinolones, polymxins, erythromycins; Tertracyclines, chloramphenicols, clindamycins, lincomycins, sulfonamides, their homologues, analogues, derivatives, pharmaceutical salts and mixtures thereof; (c) paclitaxel, docetaxel, immunosuppressants such as sirolimus or everolimus, alkylating agents including mechlorethamine, chlorambucil, cyclophosphamide, melphalan and ifosfamide; Antimetabolites including methotrexate, 6-mercaptopurine, 5-fluorouracil and cytarabine; Plant alcohols including vinblastine; Vincristine and etoposide; Antibiotics including doxorubicin,

Daunomycin, bleomycin and mitomycin; Nitrosurea including carmustine and lomustine; inorganic ions including cisplatin; biological reaction modifiers including interferon; angiostatic and endostatic agents; Enzymes including asparaginase; and hormones include tamoxifen and flutamide, their homologues, analogs, fragments, derivatives, pharmaceutical salts and mixtures thereof;

(d) antiviral agents such as amantadine, rimantadine, rabavirin, idoxuridine, vidarabine, trifluridine, acyclovir, ganciclocir, zidovudine, phosphonoformates, interferons, their homologues, analogs, fragments, derivatives, pharmaceutical salts and mixtures thereof; and e) anti-inflammatory agents such as ibuprofen, dexamethasone or methylprednisolone.

In a preferred embodiment, the coating composition to be used according to the invention in the form of a solution comprises a polyurethaneurea which is at least built up from a) at least one polycarbonate polyol; b) at least one polyisocyanate; c) at least one monofunctional polyoxyalkylene ether; d) at least one diamine or an aminoalcohol. In a further preferred embodiment of the present invention, the coating composition to be used according to the invention in the form of a solution comprises a polyurethaneurea which is at least built up from a) at least one polycarbonate polyol; b) at least one polyisocyanate; c) at least one monofunctional polyoxyalkylene ether; d) at least one diamine or an aminoalcohol; and e) at least one polyol.

In a further preferred embodiment of the present invention, the coating composition to be used according to the invention in the form of a solution comprises a polyurethaneurea which is at least built up a) at least one polycarbonate polyol; b) at least one polyisocyanate; c) at least one monofunctional polyoxyalkylene ether; d) at least one diamine or an aminoalcohol; e) at least one polyol; f) at least one further amine- and / or hydroxy-containing building block.

The coating compositions in the form of solutions to be used according to the invention preferably comprise polyurethane ureas which are at least synthesized from a) at least one polycarbonate polyol having an average molecular weight between 400 g / mol and 6000 g / mol and a hydroxyl functionality of 1.7 to 2.3 or from mixtures of such polycarbonate polyols; b) at least one aliphatic, cycloaliphatic or aromatic polyisocyanate or mixtures of such polyisocyanates in an amount per mole of the polycarbonate polyol from 1.0 to 3.5 mol; c) at least one monofunctional polyoxyalkylene ether or a mixture of such polyethers having an average molecular weight between 500 g / mol and 5000 g / mol in an amount per mole of the polycarbonate polyol of 0.01 to 0.5 mol; d) at least one aliphatic or cycloaliphatic diamine or at least one aminoalcohol as so-called chain extenders or mixtures of such compounds in an amount of from 0.1 to 1.5 mol per mole of the polycarbonate polyol; e) optionally one or more short-chain aliphatic polyols having a molecular weight between 62 g / mol and 500 g / mol in an amount per mole of the polycarbonate polyol of 0.05 to 1 mol; and f) optionally amine- or OH-containing building blocks which are located at the polymer chain ends and terminate them.

According to the invention, more preference is given in the coating composition in the form of a solution to polyurethaneureas which are at least synthesized from a) at least one polycarbonate polyol having an average molecular weight between 500 g / mol and 5000 g / mol and a hydroxyl functionality of 1.8 to 2.2 or mixtures of such polycarbonate polyols; b) at least one aliphatic, cycloaliphatic or aromatic polyisocyanate or mixtures of such polyisocyanates in an amount of from 1.0 to 3.3 mol per mole of the polycarbonate polyol; c) at least one monofunctional polyoxyalkylene ether or a mixture of such polyethers having an average molecular weight between 1000 g / mol and 4000 g / mol in an amount per mole of the polycarbonate polyol of 0.02 to 0.4 mol; d) at least one aliphatic or cycloaliphatic diamine or at least one aminoalcohol as so-called chain extenders or mixtures of such compounds in an amount of from 0.2 to 1.3 mol per mole of polycarbonate polyol; e) optionally one or more short chain aliphatic polyols having a molecular weight between 62 g / mol and 400 g / mol in an amount per mole of the polycarbonate polyol of 0.05 to 0.5 mol; and f) optionally amine- or OH-containing building blocks which are located at the polymer chain ends and terminate them.

According to the invention, polyurethane ureas in the coating solution which are at least synthesized are preferably composed of a) at least one polycarbonate polyol having an average molecular weight between 600 g / mol and 3000 g / mol and a hydroxyl functionality of 1.9 to 2.1 or from Mixtures of such polycarbonate polyols; b) at least one aliphatic, cycloaliphatic or aromatic polyisocyanate or mixtures of such polyisocyanates in an amount of from 1.0 to 3.0 mol per mole of the polycarbonate polyol; c) at least one monofunctional polyoxyalkylene ether or a mixture of such polyethers having an average molecular weight between 1000 g / mol and 3000 g / mol in an amount per mole of the polycarbonate polyol of 0.04 to 0.3 mol, wherein a mixture of polyethylene oxide and polypropylene oxide in particular is preferred; and d) at least one aliphatic or cycloaliphatic diamine or at least one aminoalcohol as so-called chain extenders or mixtures of such compounds in an amount of from 0.3 to 1.2 moles per mole of the polycarbonate polyol; and e) optionally one or more short chain aliphatic polyols having a molecular weight between 62 g / mol and 400 g / mol in an amount per mole of the polycarbonate polyol of 0.1 to 0.5 mol.

In order to produce surfaces with antifouling properties, the coating compositions to be used according to the invention may comprise the antifouling agents known from the prior art. Their presence usually enhances the already excellent antifouling properties of the surfaces produced by the coating compositions according to the invention. A coating composition in the form of a solution to be used according to the invention can be used to form a coating on a medical device. The term "medical device" is to be broadly understood in the context of the present invention Suitable, non-limiting examples of medical devices (including instruments) include contact lenses, cannulas, catheters, for example, urological catheters such as bladder catheters or ureteral catheters, central venous catheters, venous catheters, or Inlet and outlet catheters; dilation balloons, catheters for angioplasty and biopsy, catheters used for insertion of a stent, a graft or a kavafilter, balloon catheters or other expandable medical devices, endoscopes, larnygoscopes, tracheal devices such as endotracheal hoses, respirators and other tracheal suction devices, bronchoalveolar irrigation catheters, catheters used in coronary angioplasty, guide rods, introducers and the like, vascular grafts, pacemaker parts, cochlear implants, dental implant tubes for feeding, Dr nage hoses and guidewires.

In addition, the coating solutions to be used according to the invention can be used for the production of protective coatings, for example for gloves, stents and other implants, extracorporeal blood tubes (tubes), membranes, for dialysis, for example, blood filters, circulatory assist devices, bandage materials the wound care, urine bag and ostomy pouch are used. Also included are implants containing a medically effective agent, such as medicated stents or balloon surfaces or contraceptive devices. Typically, the medical device is formed from catheters, endoscopes, laryngoscopes, endotracheal tubes, feeding tubes, guide rods, stents, and other implants.

As a substrate of the surface to be coated many materials come into question, such as metals, textiles, ceramics or plastics, wherein the use of plastics for the manufacture of medical devices is preferred.

According to the invention, it has been found that medical devices with very hydrophilic and thus lubricious, blood-compatible surfaces can be produced by using aqueous, nonionically stabilized polyurethane dispersions of the type described above for coating the medical devices. The coating compositions described above are preferably obtained as an organic solution and applied to the surface of the medical devices. In addition to being used as a coating for medical devices, the coating compositions described above can also be used for other non-medical technical applications.

Substrates for applications outside medical coatings are, for example, metals, plastics, ceramics, textiles, leather, wood, paper, painted surfaces of all substrates mentioned and glasses. In this case, the coating materials can be applied directly to the substrate or alternatively to a previously applied to the substrate primer.

Thus, the coatings produced according to the invention serve as protection of surfaces from fogging with moisture, for the production of easy-to-clean or self-cleaning surfaces. These hydrophilic coatings also reduce the absorption of dirt and prevent the formation of water spots. Conceivable outdoor applications are, for example, window panes and skylights, glass facades or Plexiglas roofs. In the interior, such materials can be used for the coating of surfaces in the sanitary area. Other applications include the coating of optical glasses and lenses such as eyeglass lenses, binocular eyepiece and lens lenses, and lens lenses for cameras or packaging materials such as food packaging to prevent moisture fogging or condensed water drop formation. The coating materials to be used according to the invention are also suitable for finishing surfaces in contact with water to reduce the growth. This effect is also called antifouling effect. A very important application of this antifouling effect is in the area of underwater painting of ship hulls. Ship hulls without anti-fouling equipment are very quickly overgrown by marine organisms, which leads to a reduction of the possible speed and a higher fuel consumption due to increased friction. The coating materials according to the invention reduce or prevent the growth of marine organisms and prevent the above-described disadvantages of this growth. Further applications in the field of antifouling coatings are articles for fishing such as fishing nets and all metallic substrates in underwater use such as pipelines, oil rigs, lock chambers and gates etc. Hulls which have surfaces produced with the coating materials according to the invention, in particular below the waterline, also have one reduced frictional resistance, so that such equipped ships either have a reduced fuel consumption or reach higher speeds. This is particularly interesting in the sport boat area and yacht building.

Another important application of the above-mentioned hydrophilic coating materials is the printing industry. Hydrophobic surfaces can be According to the invention coatings are hydrophilized and are characterized printable with polar inks or can be applied by means of inkjet technology.

Another field of application of the hydrophilic coatings according to the invention are formulations for cosmetic applications. Active substance-releasing systems based on the hydrophilic coating materials according to the invention are also conceivable outside medical technology, for example for applications in crop protection as carrier material for active ingredients. The entire coating can then be regarded as an active substance-releasing ssystem and be used, for example, for coating seed (seed grains). Due to the hydrophilic properties of the coating, the active ingredient contained in the moist soil can escape and develop its intended effect without the germination of the seed is impaired. In the dry state, however, the coating agent safely binds the active substance to the seed, so that, for example, when the seed is injected into the soil with the spreading machine, the active substance is not detached, as a result of which it produces undesired effects, e.g. could develop on the existing fauna (bee endangerment by insecticides, which are supposed to prevent the insect infestation of the seed in the soil).

In particular, coating solutions are preferred which are composed of a mixture of polycarbonate polyols and a monofunctional polypropylene oxide-polyethylene oxide alcohol.

Preparation of the coating solutions

In the context of the present invention, it is particularly preferred that the coatings of the medical devices are prepared starting from solutions of the coating composition described in more detail above.

According to the invention, it has been found that the resulting coatings differ on medical devices, depending on whether the coating composition described above is prepared from a dispersion or a solution. In this case, the coatings according to the invention have advantages on medical devices if they are obtained starting from solutions of the above-described coating compositions.

Without wishing to be bound by theory, it is assumed according to the invention that, because of the particulate structure of the polyurethanes in aqueous dispersion, the film formation of the polymers is not complete. In the films, the particle structures are usually still detectable, for example by Atomic Force Microscopy (AFM). Polyurethanes from solution provide smoother coatings. Due to the intimate behavior When the polyurethane molecules are agglomerated and entangled in organic solution, the dried films are also stronger in tensile strength and more resistant to storage in water.

The medical devices according to the invention can be coated by means of various methods with the hydrophilic polyurethane solutions. Suitable coating techniques include, for example, doctoring, printing, transfer coating, spraying, spin coating or dipping.

The organic polyurethane solutions can be prepared by any method.

However, the following procedure has been found to be preferred: To prepare the polyurethaneurea solutions to be used according to the invention, it is preferred to react the polycarbonate polyol, the polyisocyanate, the monofunctional polyether alcohol and optionally the polyol in the melt or in solution until all the hydroxyl groups have been consumed

The stoichiometry used in this case between the individual structural components involved in the reaction results from the aforementioned quantitative ratios.

The reaction takes place at a temperature of preferably between 60 and 110 ⁰ C, particularly preferably 75 to 110 ° C, particularly 90 to 110 ° C, with temperatures of 110 ° C is preferred because of the speed of the reaction. Higher temperatures can also be used, but there is a risk in individual cases and depending on the individual components used that decomposition processes and discoloration occur in the resulting polymer.

In the prepolymer of isocyanate and all hydroxyl-containing components, the reaction in melt is preferred, but there is a risk that it comes to high viscosities of the reacted mixtures. In these cases, it is also advisable to add solvents. However, it should preferably not contain more than about 50 wt .-% of solvent, otherwise the dilution significantly slows down the reaction rate.

In the reaction of isocyanate and the hydroxyl-containing components, the reaction in the melt can take place in a period of 1 hour to 24 hours. Low addition of solvent leads to a slowdown, but the reaction periods are within the same time periods.

The order of addition or conversion of the individual constituents may differ from the sequence indicated above. This may be particularly advantageous if the mechanical properties of the resulting coatings to be changed. If, for example, all hydroxyl-containing components are reacted simultaneously, a mixture of hard and soft segments is formed. For example, if the low molecular weight polyol is selected after the polycarbonate-polyol component te gives, you get defined blocks, which can bring other properties of the resulting coatings with it. Thus, the present invention is not limited to any order of addition or reaction of the individual components of the polyurethane coating. Then, further solvent is added and the optionally dissolved chain extender diamine or the dissolved chain extender amino alcohol (synthesis component (d)) is added.

The further addition of the solvent is preferably carried out stepwise, so as not to slow down the reaction unnecessarily, which would happen if the amount of solvent were completely added, for example at the beginning of the reaction. Furthermore, it is bound at a high content of solvent at the beginning of the reaction at a relatively low temperature, which is at least co-determined by the nature of the solvent. This also leads to a slowing of the reaction.

After reaching the target viscosity, the remaining residues of NCO can be blocked by a mono-functional aliphatic amine. The remaining isocyanate groups are preferably blocked by reaction with the alcohols contained in the solvent mixture.

Suitable solvents for the preparation and use of the polyurethaneurea solutions according to the invention are all conceivable solvents and solvent mixtures such as dimethylformamide, N-methylacetamide, tetramethylurea, N-methylpyrrolidone, aromatic solvents such as toluene, linear and cyclic esters, ethers, ketones and Alcohols in question. Examples of esters and ketones are, for example, ethyl acetate, butyl acetate, acetone, γ-butyrolactone, methyl ethyl ketone and methyl isobutyl ketone.

Preference is given to mixtures of alcohols with toluene. Examples of the alcohols used together with the toluene are ethanol, n-propanol, iso-propanol and 1-methoxy-2-propanol.

In general, in the reaction so much solvent is used, that about 10 to 50 wt .-% solutions, more preferably about 15 to 45 wt .-% solutions, more preferably about 20 to 40 wt .-% solutions, receives. The solids content of the polyurethane solutions is generally between 5 to 60 wt .-%, preferably 10 to 40 wt .-%. For coating experiments, the polyurethane solutions can be diluted as desired with toluene / alcohol mixtures in order to be able to variably adjust the thickness of the coating. All concentrations of 1 to 60 wt .-% are possible, preferred are concentrations in the range 1 to 40 wt .-%. In this case, any layer thicknesses can be achieved, for example, some 100 nm up to a few 100 microns, and in the context of the present invention also higher and lower thicknesses are possible. Other additives such as antioxidants or pigments may also be used. In addition, if desired, further additives such as handle auxiliaries, dyes, matting agents, UV stabilizers, light stabilizers, water repellents and / or leveling agents may be used. Based on these solutions, medical coatings are then prepared by the methods described above.

Many substrates such as metals, textiles, ceramics and plastics can be coated. The coating of medical devices that are made of plastic or metals is preferred. Examples of metals which can be mentioned are: medical stainless steel and nickel-titanium alloys. Many polymer materials are conceivable from which the medical device can be constructed, for example polyamide; polystyrene; polycarbonate; polyether; Polyester; polyvinyl acetate; natural and synthetic rubbers; Block copolymers of styrene and unsaturated compounds such as ethylene, butylene and isoprene; Polyethylene or copolymers of polyethylene and polypropylene; Silicone; Polyvinyl chloride (PVC) and polyurethanes. For better adhesion of the hydrophilic polyurethane on the medical device, other suitable coatings can be applied as a substrate before the application of these hydrophilic coating materials.

The medical devices can be coated by various methods with the hydrophilic polyurethane dispersions. Suitable coating techniques are doctoring, printing, transfer coating, spraying, spin coating or dipping.

In addition to the hydrophilic properties of improving lubricity, the layers produced according to the invention to be used coating compositions are characterized by a high blood compatibility. As a result, working with these coatings is particularly advantageous in blood contact. The materials show reduced coagulation tendency in blood contact compared to prior art polymers.

The advantages of the catheters provided with the hydrophilic polyurethane coatings obtained by the use of the invention are set forth by comparative experiments in the following examples. Examples

The NCO content of the resins described in the Examples and Comparative Examples was determined by titration in accordance with DIN EN ISO 11909.

The solids contents were determined in accordance with DIN-EN ISO 3251. 1 g of polyurethane dispersion was dried at 115 ° C. to constant weight (15-20 min) using an infrared drier.

The measurement of the average particle sizes of the polyurethane dispersions is carried out using the High Performance Particle Sizer (HPPS 3.3) from Malvem Instruments.

Unless otherwise indicated, the amounts stated in% are by weight and relate to the resulting aqueous dispersion.

Viscosity measurements were carried out with the Physics MCR 51 Rheometer from Anton Paar GmbH, Ostfildern, Germany.

Substances used and abbreviations:

Desmophen ^® C2200: polycarbonate polyol, OH number 56 mg KOH / g, number average molecular weight 2000 g / mol (Bayer MaterialScience AG, Leverkusen, DE)

Desmophen ^® C 1200: polycarbonate polyol, OH number 56 mg KOH / g, number average molecular weight 2000 g / mol (Bayer MaterialScience AG, Leverkusen, DE)

Desmophen ^® XP 2613 polycarbonate polyol, OH number 56 mg KOH / g, number average molecular weight 2000g / mol (Bayer Material Science AG, Leverkusen, DE)

PolyTHF ^v 2000: polytetramethylene glycol polyol, OH number 56 mg KOH / g, number average molecular weight 2000 g / mol (BASF AG, Ludwigshafen, DE)

^® polyether LB 25: (monofunctional polyether based on ethylene oxide / propylene oxide-based number average molecular weight 2,250 g / mol, OH number 25 mg KOH / g (Bayer MaterialScience AG, Leverkusen, DE) Example 1 :

Preparation of a polyurethaneurea solution according to the invention:

198.6 g of Desmophen ^® C 2200, 23.0 g LB 25 and 47.8 g of 4,4'-bis (isocyanatocyclohexyl) - methane (Hi ₂ MDI) were reacted at 110 ° C in the melt to a constant NCO Content of 2.4% implemented. It was allowed to cool and diluted with 350.0 g of toluene and 200 g of iso-propanol. At room temperature, a solution of 12.5 g of isophorone diamine in 95.0 g of 1-methoxy-2-propanol was added. After completion of the molecular weight and reaching the desired viscosity range (check by measuring the viscosity of a pulled sample with the above-cited rheometer) was stirred for another 4 hours to block the residual isocyanate content with iso-propanol. 927 g of a 30.4% was obtained solution of polyurethaneurea in toluene / iso-propanol / 1-methoxy-2 having a viscosity of 19600 mPas at 22 ⁰ C.

Example 2 Preparation of a Polyurethaneurea Solution According to the Invention

195.4 g of Desmophen ^® C 2200, 30.0 g LB 25 and 47.8 g of 4,4'-bis (isocyanatocyclohexyl) - methane (Hi ₂ MDI) were reacted at 110 ° C until a constant NCO content of 2 , 3% implemented. It was allowed to cool and diluted with 350.0 g of toluene and 200 g of iso-propanol. At room temperature, a solution of 12.7 g of isophoronediamine in 94.0 g of 1-methoxy-2-propanol was added. After completion of the molecular weight and reaching the desired viscosity range was stirred for another 4 hours to block the residual isocyanate content with iso-propanol. 930 g of a 30.7% strength polyurethane urea solution in toluene / isopropanol / 1-methoxy-2-propanol having a viscosity of 38,600 mPas at 22 ° C. were obtained.

Example 3:

Preparation of a polyurethaneurea solution according to the invention:

195.4 g of Desmophen ^® XP 2613, 30.0 g LB 25 and 47.8 g of 4,4'-bis (isocyanatocyclohexyl) - methane (Hi ₂ MDI) were reacted at 110 ⁰ C until a constant NCO content of 2 , 4% implemented. It was allowed to cool and diluted with 350.0 g of toluene and 200 g of iso-propanol. At room temperature, a solution of 12.7 g of isophoronediamine in 95.0 g of 1-methoxy-2-propanol was added. After completion of the molecular weight and reaching the desired viscosity range was stirred for another 4 hours to block the residual isocyanate content with iso-propanol. 931 g of a 30.7% strength polyurethane urea solution in toluene / isopropanol / 1-methoxypropanol-2 having a viscosity of 26,500 mPas at 22 ° C. were obtained. Example 4:

Preparation of a polyurethaneurea solution according to the invention:

198.6 g of Desmophen ^® C 1200, 23.0 g LB 25 and 47.8 g of 4,4'-bis (isocyanatocyclohexyl) - methane (Hi ₂ MDI) were reacted at 110 ° C until a constant NCO content of 2 , 4% implemented. It was allowed to cool and diluted with 350.0 g of toluene and 200 g of iso-propanol. At room temperature, a solution of 13.2 g of isophoronediamine in 100.0 g of 1-methoxy-2-propanol was added. After completion of the molecular weight and reaching the desired viscosity range was stirred for another 4 hours to block the residual isocyanate content with iso-propanol. This gave 933 g of a 30.3% strength polyurethane urea solution in toluene / isopropanol / 1-methoxy-2-propanol having a viscosity of 17,800 mPas at 22 ° C.

Example 5:

Preparation of a polyurethaneurea solution according to the invention: 195.4 g Desmophen ^® C 1200, 30.0 g LB 25 and 47.8 g of 4,4'-bis (isocyanatocyclohexyl) - methane (Hi ₂ MDI) were reacted at 110 ° C to a constant NCO content of 2.4% implemented. It was allowed to cool and diluted with 350.0 g of toluene and 200 g of iso-propanol. At room temperature, a solution of 11.8 g of isophoronediamine in 94.0 g of 1-methoxy-2-propanol was added. After completion of the molecular weight and reaching the desired viscosity range, stirring was continued for a further 4 hours in order to block the residual isocyanate content with isopropanol. 931 g of a 30.7% strength polyurethane urea solution in toluene / isopropanol / 1-methoxypropanol-2 having a viscosity of 23,700 mPas at 22 ° C. were obtained.

Example 6;

Preparation of a polyurethaneurea solution as a comparison product to the inventive Example 1. The Desmophen ^® C2200 is replaced by the PolyTHF 2000th

194.0 g of polyTHF 2000, 22.6 g of LB 25 and 47.8 g of 4,4'-bis (isocyanatocyclohexyl) methane (Hi ₂ MDI) were added at 110 ° C. to a constant NCO content of 2.3%. implemented. It was allowed to cool and diluted with 350.0 g of toluene and 200 g of iso-propanol. At room temperature, a solution of 12.1 g of isophoronediamine in 89.0 g of 1-methoxy-2-propanol was added. After completion of the molecular weight and reaching the desired viscosity range, stirring was continued for a further 4 hours in order to block the residual isocyanate content with isopropanol. 916 g of a 30.2% strength polyurethane urea solution in toluene / isopropanol / 1-methoxypropanol-2 having a viscosity of 15200 mPas at 22 ° C. were obtained. Example 7:

Preparation of a polyurethaneurea solution as a comparison product to the inventive Example 2. The Desmophen ^® C2200 is replaced by the PolyTHF 2000th 190.6 g of polyTHF 2000, 30.0 g of LB 25 and 47.8 g of 4,4'-bis (isocyanatocyclohexyl) methane (Hi ₂ MDI) were added at 110 ° C. to a constant NCO content of 2.3%. implemented. It was allowed to cool and diluted with 350.0 g of toluene and 200 g of iso-propanol. At room temperature, a solution of 12.1 g of isophoronediamine in 89.0 g of 1-methoxy-2-propanol was added. After completion of the molecular weight and reaching the desired viscosity range, stirring was continued for a further 4 hours in order to block the residual isocyanate content with isopropanol. 919 g of a 30.5% strength polyurethane urea solution in toluene / isopropanol / 1-methoxypropanol-2 having a viscosity of 21,000 mPas at 22 ° C. were obtained.

Example 8: Preparation of the coatings and measurement of the static contact angle

The static contact angle measurements were made on 25x75 mm glass slides using a spincoater (RC5 Gyrset 5, Karl Suess, Garching, Germany). A slide was clamped on the sample plate of the spin coater and homogenously covered with about 2.5-3 g of organic 15% strength polyurethane solution. All organic polyurethane solutions were mixed with a solvent mixture of 65% by weight of toluene and 35% by weight of isopropanol to a polymer content of 15% by weight diluted. By rotating the sample tray for 20 sec at 1300 rpm, a homogeneous coating was obtained which was dried at 100 ° C for 1 h and then at 50 ° C for 24 h. The resulting coated slides were subjected directly to a contact angle measurement.

From the resulting coatings on the slides, a static contact angle measurement was performed. By means of the video angle angle measuring device OCA20 from Dataphysics with computer-controlled syringes, 10 drops of Millipore water were placed on the sample and their static wetting edge angle was measured. Previously, the static charge (if any) on the sample surface was removed using an antistatic hair dryer. Table 1: Static contact angle measurements

As shown in Table 1, the polycarbonate-containing coatings of Examples 1-5 give highly hydrophilic coatings with static contact angles <40 °. In contrast, the polyTHF-containing coatings 7-9 are substantially more non-polar, although the composition of these coatings are otherwise identical to those of Examples 1 and 2.

Example 9:

This comparative example describes the synthesis of a polyurethane urea polymer which, instead of the mixed monofunctional polyethylene-polypropylene oxide alcohol LB 25, contains the same molar proportion of a pure monofunctional polyethylene oxide alcohol. The polymer is identical to that of Example 1 except that it contains a different terminal group. The synthesis in toluene and alcohols as described in Examples 1-7 does not work when using this alcohol. Therefore, the synthesis is carried out in pure dimethylformamide (DMF).

198.6 g of Desmophen ^® C 2200, 20.4 g of polyethylene glycol 2000 monomethyl ether (source: Fluka, Product No. 81,321th), and 47.8 g of 4,4'-bis (isocyanatocyclohexyl) methane were (H ₁₂ MDI) reacted at 110 ° C in the melt to a constant NCO content of 2.4%. It was allowed to cool and diluted with 550 g of DMF. At room temperature, a solution of 10.5 g of isophoronediamine in 100 g of DMF was added. After completion of the molecular weight and reaching the desired viscosity range (checking by measuring the viscosity of a pulled sample with the above-cited rheometer) was added 1.0 g of n-butylamine to block the remaining low isocyanate content. This gave 927 g of a 29.8% polyurethaneurea solution in dimethylformamide having a viscosity of 22,700 mPas at 23 ° C. Example 10;

Synthesis of a polyurethaneurea polymer according to the invention in DMF as solvent. The polymer is identical to that of Example 1, but was therefore made in DMF to compare its physical properties with the polymer of Example 9.

198.6 g of Desmophen ^® C 2200, 23.0 g LB 25 and 47.8 g of 4,4'-bis (isocyanatocyclohexyl) - methane (H ₁₂ MDI) were reacted at 110 ° C in the melt to a constant NCO Content of 2.4% implemented. It was allowed to cool and diluted with 550 g of DMF. At room temperature, a solution of 10.5 g of isophoronediamine in 100 g of 1-methoxy-2-propanol was added. After completion of the molecular weight and reaching the desired viscosity range (check by measuring the viscosity of a pulled sample with the above-cited rheometer) was added to 0.5 g of n-butylamine to block the low residual isocyanate content with iso-propanol. 930 g of a 30.6% strength polyurethaneurea solution in DMF having a viscosity of 16,800 mPas at 23 ° C. were obtained.

Example 11:

As described in Example 8, the polyurethane solutions of Examples 9 and 10 were used to produce films on glass and to measure static contact angles.

Table 2: Static contact angles depending on the monofunctional polyethers used

The film of Example 10 produced with the mixed (polyethylene oxide / polypropylene oxide) monofunctional polyether alcohol shows at 36 ° a significantly lower static contact angle than the film of Example 9 (55 °) which contains pure polyethylene oxide units.

Example 12: Synthesis of a polyurethane according to the invention in organic solution. This product was compared with the appropriately aqueous-prepared polyurethane of Example 13 (see Example 14). 277.2 g of Desmophen ^® C 2200, 33.1 g LB 25, 6.7 g of neopentyl glycol, 71.3 g of 4,4'-bis (iso-cyanatocyclohexyl) methane (MDI Hi ₂₎ and 11.9 g of isophorone diisocyanate reacted at 110 ° C to a constant NCO content of 2.4%. It was allowed to cool and diluted with 500.0 g toluene and 350.0 g iso-propanol. At room temperature, a solution of 6.2 g of isophoronediamine in 186.0 g of 1-methoxy-2-propanol was added. After completion of the molecular weight and reaching the desired viscosity range was stirred for another 4 hours to block the residual isocyanate content with isopropanol. This gave 1442 g of a 28.6% polyurethaneurea solution in toluene / isopropanol / 1-methoxypropanol-2 having a viscosity of 17500 mPas at 23 ° C.

Example 13:

Synthesis of the polyurethane of Example 12 in aqueous dispersion. It consists of the same polymer as described in Example 12. Both polymers are compared in Example 14 with each other.

277.2 g of Desmophen ^® C 2200, 33.1 g of polyether LB 25 and 6.7 g of neopentyl glycol were introduced at 65 ° C and homogenized for 5 min with stirring. To this mixture was added at 65 ° C within 1 min, first 71.3 g of 4,4'-bis (isocyanatocyclohexyl) methane (Hi ₂ MDI) and then 11.9 g of isophorone diisocyanate. The mixture was heated to 110 ° C until a constant NCO value of 2.4% was reached. The finished prepolymer was dissolved at 50 ° C in 711 g of acetone and then added at 40 ° C, a solution of 4.8 g of ethylenediamine in 16 g of water within 10 min. The stirring time was 5 min. The mixture was then dispersed within 15 minutes by adding 590 g of water. This was followed by removal of the solvent by distillation in vacuo. A storage-stable polyurethane dispersion with a solids content of 40.7% and an average particle size of 136 nm was obtained. The pH of this dispersion was 6.7.

Example 14:

The two coatings of Examples 12 and 13 were applied to release paper with a 200 μm doctor blade. The coating of Example 12 was applied in undiluted form, the aqueous dispersion was added prior to film formation with 2 wt% of a thickener (Borchi Gel ^® A LA, Fa. Borchers, Langenfeld, Germany) and 30 min at RT homogenized by stirring. The wet films were dried at 100 ^° C. for 15 minutes. Tensile strength and elongation at break are measured in the dry state and after 24 h watering of the films. The investigations were carried out in accordance with DIN 53504. Table 3: Comparison of Tensile Results for Polyurethane from Organic Solution and Aqueous Dispersion

The results of the table show that the breaking stress of the dried films for both polyurethanes, regardless of preparation as a solution or as an aqueous dispersion, are within experimental accuracy. However, the organic solution film of Example 12 has higher elasticity (700% elongation at break as compared to 550% for the aqueous dispersion polymer). In addition, breaking stress and elongation at break for the organic solution-made film do not change within the measurement accuracy, while breaking stress and breaking elongation of the film prepared from aqueous dispersion decrease significantly.

Claims

Patentansprtiche:

1. Use of a coating composition in the form of a solution containing at least one polyurethaneurea terminated with a copolymer unit of polyethylene oxide and polypropylene oxide for coating substrates.

2. Use according to claim 1, characterized in that the polyurethaneurea has units which are based on polycarbonate containing at least one hydroxyl group.

3. Use according to claim 1 or 2, characterized in that the polyurethaneurea has units which are based on aliphatic or cycloaliphatic polyisocyanates.

4. Use according to one of claims 1 to 3, characterized in that the polyurethaneurea has units which are based on at least one polyol.

5. Use according to one of claims 1 to 4, characterized in that the polyurethaneurea has units which go back to at least one diamine or amine alcohol.

6. Use according to any one of claims 1 to 5, characterized in that the polyurethaneurea has units which are based on further hydroxyl- and / or amine-containing synthesis components.

7. Use according to one of claims 1 to 6, characterized in that the polyurethaneurea is at least built up from the following structural components a) at least one polycarbonate polyol; b) at least one polyisocyanate; c) at least one monofunctional polyoxyalkylene ether; and d) at least one diamine or an aminoalcohol.

8. Use according to one of claims 1 to 7, characterized in that polyurethaneurea additionally comprises structural components from e) at least one polyol.

9. Use according to one of claims 1 to 8, characterized in that the polyurethaneurea is at least built up from the following Aufbaukom- components: a) at least one polycarbonate polyol having an average molecular weight between

400 g / mol and 6000 g / mol and a hydroxyl functionality of 1.7 to 2.3 or of mixtures of such polycarbonate polyols; b) at least one aliphatic, cycloaliphatic or aromatic polyisocyanate or mixtures of such polyisocyanates in an amount per mole of the polycarbonate natpolyols of 1.0 to 3.5 mol; c) at least one monofunctional polyoxyalkylene ether or a mixture of such polyethers having an average molecular weight between 500 g / mol and 5000 g / mol in an amount per mole of the polycarbonate polyol of 0.01 to 0.5 mol; d) at least one aliphatic or cycloaliphatic diamine or at least one aminoalcohol as so-called chain extenders or mixtures of such compounds in an amount of from 0.1 to 1.5 mol per mole of the polycarbonate polyol; and e) optionally one or more short-chain aliphatic polyols having a molecular weight between 62 g / mol and 500 g / mol in an amount per mole of the polycarbonate polyol of 0.05 to 1.0 mol.

Use according to any one of claims 1 to 9, comprising the steps of A) preparing a coating composition by:

(I) reacting the polycarbonate polyol, the polyisocyanate and the monofunctional polyoxyalkylene ether and optionally the polyol in the melt or in the presence of a solvent in solution until all the hydroxyl groups have been consumed;

(H) addition of further solvent and, if appropriate, addition of the dissolved diamine or the optionally dissolved aminoalcohol; and (HI) optionally blocking the remaining after reaching the target viscosity residues of NCO groups by a monofunctional aliphatic amine and

B) coating a substrate with the coating composition obtained according to (A).

11. Use according to claim 10, characterized in that the solvent is selected from the group consisting of dimethylformamide, N-methylacetamide, tetramethylurea, N-methylpyrrolidone, γ-butyrolactone, aromatic solvents Mittein, linear and cyclic esters, ethers, ketones , Alcohols and mixtures thereof.

12. Use according to claim 10 or 11, characterized in that the solids content of the polyurethane solution is between 5 to 60 wt .-%.

13. Use according to one of claims 1 to 12 for coating at least one medical device.

14. Use according to one of claims 1 to 12 for the coating of technical substrates in the non-medical field.

15. Use according to one of claims 1 to 12 for the production of easy-to-clean or self-cleaning surfaces.

16. Use according to one of claims 1 to 12 for coating Verschei- conditions and optical glasses and lenses.

17. Use according to one of claims 1 to 12 for the coating of substrates in the sanitary sector.

18. Use according to one of claims 1 to 12 for coating packaging materials.

19. Use according to any one of claims 1 to 12 for reducing the growth of the coated surfaces.

20. Use according to one of claims 1 to 12 for the coating of over- and underwater substrates for reducing the frictional resistance of the substrates to water.

21. Use according to one of claims 1 to 12 for printing preparation of substrates.

22. Use according to one of claims 1 to 12 for the preparation of formulations for cosmetic applications.

23. Use according to one of claims 1 to 12 for the production of active substance-spreading systems for coating seeds.