EP2285855A1

EP2285855A1 - Hydrophilic polyurethane coatings

Info

Publication number: EP2285855A1
Application number: EP09753632A
Authority: EP
Inventors: Jürgen Köcher; Thorsten Rische
Original assignee: Bayer MaterialScience AG
Current assignee: Bayer Intellectual Property GmbH
Priority date: 2008-05-28
Filing date: 2009-05-19
Publication date: 2011-02-23
Also published as: CN102046682A; JP2011524431A; US20110078832A1; DE102008025613A1; WO2009143977A1

Abstract

The invention relates to the use of specific polyurethane urea coatings for coating substrates, the polyurethane urea (1) being terminated by a copolymer unit which is constituted of polyethylene oxide and polypropylene oxide, and (2) comprising at least one hydroxyl group-containing polycarbonate polyol.

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 for the protection of

Surfaces before fogging, for easy to clean or self-cleaning

Surfaces and to reduce the dirt accumulation 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 dispersions according to the invention which are no longer grown to a considerable 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 watering of the equipment before the intervention can be made to reduce the friction by the formation of a homogeneous water film. Affected patients have less pain and the risk of injury to the vessel walls is thereby reduced. In addition, when using catheters in blood contact, there is always a 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.

DE-A 199 14 882 relates to polyurethanes, polyurethane ureas or polyureas in dispersed or dissolved form, which are composed of

(a) at least one polyol component,

(b) at least one di-, tri- and / or polyisocyanate component,

(c) at least one hydrophilic, nonionic or potentially ionic synthesis component consisting of compounds having at least one isocyanate-reactive group and at least one hydrophilic polyether chain and / or compounds having at least one optionally at least partially neutralized group capable of salt formation and at least one isocyanate-reactive group,

(D) at least one of (a) to (c) different structural component of the molecular weight range 32 to 500 with at least one isocyanate-reactive group and

(e) at least one monofunctional blocking agent.

The thus necessarily a monofunctional blocking agent having polymer dispersion are used for example in sizings.

DE-A 199 14 885 relates to dispersions based on polyurethanes, polyurethane-polyureas or polyureas which preferably are reaction products of a) at least one polyol component, b) at least one di-, tri- and / or polyisocyanate component, c) optionally at least one (potential) ionic synthesis component consisting of compounds having at least one group which is reactive toward NCO groups and at least one group which is optionally at least partially neutralized, capable of forming salts, d) optionally at least one nonionically hydrophilic synthesis component, consisting of in the sense of the isocyanate addition reaction e) optionally at least one of a) to d) different synthesis component of the molecular weight range from 32 to 2500 with groups reactive toward isocyanate groups and mono- to tetrafunctional, at least one hydrophilic polyether chain f) 0.1 to 15 wt .-% of at least one monofunctional blocking agent which consists of at least 50% dimethylpyrazole, wherein the sum of a) to f) is 100% and wherein either c) or d) can not be 0, and be used in such an amount that a stable dispersion is formed. The dispersions are used, among other things, for coating mineral substrates, for painting and sealing wood and wood-based materials, for painting and coating metallic surfaces, for coating and coating plastics, and for coating textiles and leather.

These polyurethaneurea dispersions known in the art are not used for medical purposes, i. for coating medical devices.

In addition, the previously known polyurethaneurea coatings often have drawbacks in that they are not sufficiently hydrophilic for use as a coating of medical devices. In this context, US Pat. No. 5,589,563 recommends surface-modified end groups for biomedical polymers which can be used to coat medical devices. These polymers include various end groups selected from amines, fluorinated alkanols, polydimethylsiloxanes and amine-terminated polyethylene oxides. However, these polymers also have no satisfactory properties as a coating for medical devices, especially with regard to the required hydrophilicity.

It is an object of the present invention to provide polyurethane-urea dispersions which can be used to coat or coat medical devices having hydrophilic surfaces. Since these surfaces are frequently used in blood contact, the surfaces of these materials should also have a good blood compatibility and in particular reduce the risk of the formation of blood clots.

The subject of this invention, therefore, is the use of certain polyurethaneurea dispersions for the production of hydrophilic surfaces, as desired for the equipment of medical devices and surfaces with antifouling properties.

The polyurethaneurea dispersions to be used according to the invention are characterized in that they

(1) at least one polyurethaneurea terminated with a copolymer unit of polyethylene oxide and polypropylene oxide, and

(2) comprise at least one polycarbonate polyol. It has been found that compositions of these specific polyurethane ureas are eminently suitable as coatings having hydrophilic properties, such as those used in many medical devices to improve the delivery properties while reducing the risk of blood clots during treatment with the medical device and to produce Surfaces with anti-fouling properties, such as in shipbuilding, are desirable.

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

(A) at least two urethane groups-containing repeat units of the following general structure

O

- N- ¹ ^ -O- H and

(b) at least one repeating unit containing urea groups

O

N- N- H H

exhibit.

The coating compositions to be used according to the invention are based on polyurethane ureas which have substantially no ionic modification. In the context 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.

The term "substantially no ionic modification" in the context of the present invention means that an ionic modification at most in a proportion of 2.50 wt .-%, preferably at most 2.00 wt .-%, in particular at most 1.50 Wt .-%, more preferably at most 1.00 wt .-%, especially at most 0.50 wt .-%, is present, it being most preferred if there is no ionic modification of the present invention intended polyurethane urea.

The polyurethane ureas according to the invention are preferably substantially linear molecules, but may also be branched. Under substantially linear molecular In the context of the present invention, len is understood as meaning slightly crosslinked systems which have a polycarbonate polyol 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 , Such systems can still be dispersed to a sufficient extent. The number average molecular weight of the polyurethane ureas preferably used according to the invention is preferably from 1000 to 200,000, particularly preferably from 5000 to 100,000. The number average molecular weight is measured against polystyrene as standard in dimethylactamide at 30 ° C.

polyurethane ureas

The polyurethane ureas according to the invention are described in more detail below.

The polyurethane ureas according to the invention are prepared by reacting synthesis components which comprise at least one polycarbonate polyol component, a polyisocyanate component, a polyoxyalkylene ether component, a diamine and / or amino alcohol component and optionally a polyol component.

In the following, the individual components are described in more detail.

(a) polycarbonate polyol

The polyurethaneurea according to the invention comprises units which are based on at least one hydroxyl-containing polycarbonate (polycarbonate polyol).

Basically suitable for introducing units based on a hydroxyl-containing polycarbonate are polycarbonate polyols, d. H. Polyhydroxyverbindungen gene, having an average hydroxyl functionality of 1.7 to 2.3, preferably from 1.8 to 2.2, more preferably from 1.9 to 2.1. The polycarbonate is thus preferably substantially linear and has only a slight three-dimensional crosslinking.

Suitable polycarbonates containing hydroxyl groups are polycarbonates of molecular weight (molecular weight determined by the OH number, DIN 53240) of preferably 400 to 6000 g / mol, more preferably 500 to 5000 g / mol, in particular 600 to 3000 g / mol for example, by reaction of carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene, with polyols, preferably diols. 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 40 to 100 wt .-% of hexanediol, preferably 1,6-hexanediol and / or hexanediol derivatives, preferably those which in addition to terminal OH groups ether or ester groups, for example products which by reaction of 1 mol Hexanediol with at least 1 mole, preferably 1 to 2 moles of caprolactone or by etherification of hexanediol with itself to di- or trihexylenglycol were obtained. 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. As butane-1,4-diol or ε-caprolactone. Further preferred polycarbonate diols are those based on mixtures of hexanediol-1,6 and butanediol-IA

(b) polyisocyanate

The polyurethaneurea according to the invention also has units which are based on at least one polyisocyanate.

As polyisocyanates (b) it is possible to use all aromatic, araliphatic, aliphatic and cycloaliphatic isocyanates known to the person skilled in the art of a middle NCO group.

Functionality> 1, preferably> 2 individually or in any mixtures with each other are used, and it is irrelevant whether these after phosgene or phosgene free

Procedures were made. These may also 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, for example bis (isocyanatoalkyl) ethers, bis- and tris- (isocyanatoalkyl) benzenes, -toluenes, and -xylols, propane diisocyanates , Butane diisocyanates, pentane diisocyanates, hexanediisocyanates (eg hexamethylene diisocyanate, HDI), heptane diisocyanates, octane diisocyanates, nonane diisocyanates (eg trimethyl-HDI (TMDI) generally as a mixture of the 2,4,4- and 2,2,4-isomers ), Nonanetriisocyanates (eg 4-isocyanatomethyl-l, 8-octanediisocyanate), decane diisocyanates, decane triisocyanates, undecane diisocyanates, undecanediisocyanates, dodecane diisocyanates, dodecane triisocyanates, 1,3- and 1,4-bis (isocyanato) methyl) cyclohexane (H ₆ XDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate, IPDI), bis (4-isocyanatocyclohexyl) methane (H ₁₂ 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 (IPDI), 1,3- and 1,4 -bis (isocyanatomethyl) cyclohexane (H _east XDI), bis (isocyanatomethyl) norbornane (NBDI), (3) 4-methyl-1 -Isocyanatomethyl- cyclohexyliso- cyanate (IMCI) and / or 4,4'-bis (isocyanatocyclohexyl ) methane (Hi ₂ 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 according to the invention is preferably 1.0 to 4.0 mol, particularly preferably 1.2 to 3.8 mol, in particular 1.5 to 3.5 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 according to the invention has units which are based on a copolymer of polyethylene oxide and polypropylene oxide. These copolymer units are present as end groups in the polyurethaneurea.

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, more 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 demonstrate 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 according to the invention has units which are based on at least one diamine or an aminoalcohol. To produce the polyurethane coatings according to the invention so-called chain extenders (d) are used. Such chain extenders are di- or polyamines and also hydrazides, eg hydrazine, 1,2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, mixture of isomers of 2, 2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 1,3- and 1,4-xylylenediamine, α, α, α ', α'-tetramethyl-I, 3- and -1, 4-xylylenediamine and 4,4-diaminodicyclohexylmethane, dimethylethylenediamine, hydrazine, adipic acid dihydrazide, 1,4-bis (aminomethyl) cyclohexane, 4,4'-diamino-3,3'-dimethyldicyclohexylme- and other (C 1 -C ₄ ) -di- and tetraalkyldicyclohexylmethanes, for example 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 constituent (d) of the coating composition to be used according to the invention can be used in its preparation as chain extender and / or as chain terminating. The amount of component (d) in the coating composition to be used according to the invention is preferably 0.05 to 3.0 mol, more preferably 0.1 to 2.0 mol, in particular 0.2 to 1.5 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 polyurethaneurea according to the invention additionally comprises units which are based on at least one further polyol.

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. Examples include the low molecular weight polyols having up to about 20 carbon atoms per molecule, such as ethylene glycol, 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), as well as trimethylolpropane, glycerol or pentaerythritol and mixtures of these and optionally also other low molecular weight polyols. Also, ester diols such as α-hydroxybutyl-ε-hydroxy-capronsäureester, ω-hydroxyhexyl-γ-hydroxybutyric acid ester, adipic acid (ß-hydroxyethyl) ester or terephthalic acid bis (ß-hydroxyethyl) ester can be used. The amount of component (e) in the coating composition to be used according to the invention is preferably 0.1 to 1.0 mol, more preferably 0.2 to 0.9 mol, in particular 0.2 to 0.8 mol, in each case based on the component (a) of the coating composition to be used according to 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. By dispersing in water, residues of isocyanate groups are hydrolyzed to amine groups. However, it may be important in individual cases to block the remaining residue of isocyanate groups before dispersing the polyurethane.

The polyurethaneurea coatings provided according to the invention can therefore also contain structural components (f), which are respectively located at the chain ends and close them. These building blocks are derived, on the one hand, from monofunctional compounds reactive with NCO groups, such as monoamines, in particular monosecondary amines or monoalcohols.

Examples which may be mentioned here include ethanol, n-butanol, ethylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadecanol, methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, methylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine and suitable substituted derivatives thereof.

Since building blocks (f) are used essentially in the coatings according to the invention to destroy the NCO excess, the required amount essentially depends on the amount of NCO excess and can not be generally specified.

In a preferred embodiment of the present invention, the component (f) is dispensed with, so that the polyurethaneurea according to the invention comprises only the constituents Ie (a) to (d) and optionally the component (e). Furthermore, it is preferred if the polyurethaneurea according to the invention consists of constituents (a) to (d) and optionally of component (e), ie does not comprise any other constituent components.

(g) other ingredients

The polyurethaneurea according to the invention may moreover comprise further constituents customary for the intended purpose, such as additives and fillers. An example These include pharmacological agents and additives that promote the release of pharmacologically active substances ("drug-eluting additives"), as well as drugs.

Medicaments which can be used in the coatings according to the invention on the medical devices are generally, for example, thrombore-resistant agents, antibiotic agents, antitumor agents, growth hormones, antiviral agents, antiangiogenic agents, angiogenic agents, antimitotic agents, antiinflammatory agents, cell cycle regulating agents, genetic agents, hormones, and their homologues, derivatives, fragments, pharmaceutical salts and combinations thereof.

Specific examples of such drugs thus include thromboresistant (non-thrombogenic) agents, or other means of suppressing an acute thrombosis, stenosis or late re-stenosis of the arteries, such as heparin, streptokinase, urokinase, tissue plasminogen activator, anti-thromboxane. B ₂ agent; Anti-B-thromboglobulin, prostaglandin-E, aspirin, dipyrimidol, anti-thromboxane A ₂ agents, murine monoclonal antibody 7E3, triazolopyrimidine, ciprosten, hirudin, ticlopidine, nicorandil, etc. A growth factor may also be used as a drug or any other inhibitor of cell growth at the stenotic site may be used to inhibit intimal fibromuscular hyperplasia at the arterial stenosis site.

The drug may also consist of a vasodilator to counteract vasospasm, for example an antispasmodic 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, which is 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 controlling releasing carrier for sustained release 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, lytic 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 including tamoxifen and flutamide, their homologues, analogs, fragments, derivatives, pharmaceutical salts and mixtures thereof; and

(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 provided according to the invention comprises a polyurethaneurea which is built up from a) at least one polycarbonate polyol; b) at least one polyisocyanate; c) at least one monofunctional mixed polyoxyalkylene ether of polyethylene oxide and polypropylene oxide; and d) at least one diamine or an aminoalcohol.

To produce surfaces with antifouling properties, the coating compositions according to the invention may comprise the antifouling agents known from the prior art. Their presence intensified in usually the already excellent anti-fouling properties of the inventive coating compositions themselves generated surfaces.

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

In a further embodiment of the present invention, the coating composition to be used according to the invention comprises a polyurethaneurea, which is built up from a) at least one polycarbonate polyol; b) at least one polyisocyanate; c) at least one monofunctional mixed polyoxyalkylene ether of polyethylene oxide and polypropylene oxide; d) at least one diamine or an aminoalcohol; e) at least one polyol; and f) at least one amine- or hydroxyl-containing monomer located at the polymer chain ends.

As already mentioned, a very particularly preferred embodiment of the present invention consists in that the polyurethaneurea to be used for the preparation of the preparations to be used according to the invention consists only of constituents (a) to (d) and optionally (e).

Also preferred according to the invention are polyurethaneureas which are built up

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 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 4.0 mol per mole of the polycarbonate polyol; c) at least one monofunctional mixed polyoxyalkylene ether of polyethylene oxide and polypropylene oxide 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 amino alcohol as a so-called chain extender or mixtures of such compounds in an amount of from 0.05 to 3.0 mol per mol 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 0.1 to 1.0 mol; and f) optionally amine- or OH-containing building blocks which are located on the polymer chain ends and terminate.

Further preferred according to the invention are polyurethaneureas which are 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 1.2 to 3.8 mol per mole of the polycarbonate polyol; c) at least one monofunctional mixed polyoxyalkylene ether of polyethylene oxide and polypropylene oxide 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 amino alcohol as a so-called chain extender or mixtures of such compounds in an amount of from 0.1 to 2.0 mol per mol of the 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 0.2 to 0.9 mol; and f) optionally amine- or OH-containing building blocks which are located on the polymer chain ends and terminate. Even more preferred according to the invention are polyurethane ureas which are synthesized from 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 mixtures of such polycarbonate polyols; b) at least one aliphatic, cycloaliphatic or aromatic polyisocyanate or mixtures of such polyisocyanates in an amount of from 1.5 to 3.5 mol per mole of the polycarbonate polyol; c) at least one monofunctional mixed polyoxyalkylene ether of polyethylene oxide and polypropylene oxide or a mixture of such polyethers having an average molecular weight of between 1000 g / mol and 3000 g / mol in an amount of 0.04 to 0.3 mol per mol of the polycarbonate polyol; d) at least one aliphatic or cycloaliphatic diamine or at least one amino alcohol as a so-called chain extender or mixtures of such compounds in an amount of from 0.2 to 1.5 mol per mole of polycarbonate polyol; e) optionally one or more short-chain aliphatic polyols having a molecular weight between 62 g / mol and 200 g / mol in an amount per mole of the polycarbonate polyol of 0.2 to 0.8 mol; and f) optionally amine- or OH-containing building blocks which are located on the polymer chain ends and terminate.

The coating compositions to be used according to the invention are applied, for example, to medical devices.

The coating compositions in the form of a dispersion 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, such as urological catheters, such as bladder catheters or ureteral catheters, central venous catheters; Catheters or inlet / outlet catheters; dilation balloons; catheters for angioplasty and biopsy; catheters used for introducing a stent, a graft or a kavafilter; balloon catheters or other expandable medical devices; endoscopes; larnygoscopes; tracheal devices such as endotracheal tubes, respirators and other tracheal suction devices; bronchoalveolar irrigation catheters; catheters used in coronary angioplasty; Importers and the like; Gefaßpfropfen; Pacemaker components; Cochlear implants; Dental implant tubes for feeding, drainage hoses; and guide wires.

In addition, the coating solutions according to the invention can be used for the production of protective coatings, for example for gloves, stents and other implants; extracorporeal (out-of-body) blood tubes (blood guide tubes); Membrane, for example for dialysis; Blood filter; Apparatus for circulatory support; Dressings for wound care; Urine bag and ostomy bag 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 it is possible to produce medical devices with very hydrophilic and thus lubricious, blood-compatible surfaces 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 aqueous dispersions 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 technical applications in the non-medical field.

Substrates for applications outside of 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 obtained in accordance with the invention serve to protect surfaces from fogging with moisture, to produce easily cleaned or self-cleaning surfaces. These hydrophilic coatings also reduce the absorption of dirt and prevent the formation of water spots. Conceivable applications in outdoor areas are, for example, window panes and skylights, glass facades or Plexiglas roofs. Indoors, such materials can be used for the coating of surfaces in the sanitary area. Further applications are the coating of optical glasses and lenses, such as spectacle lenses. lenses, lenses and lens lenses for cameras or packaging materials such as food packaging to prevent moisture build-up 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 hydrophilized by the coatings according to the invention and are thereby printable with polar printing inks or can be applied by means of inkjet technology.

Another field of application of the hydrophilic coatings used according to the invention are formulations for cosmetic applications.

Drug-releasing systems based on the hydrophilic coating materials of the invention are also conceivable outside of medical technology, for example for applications in crop protection as a 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 injecting the seed with the application machine into the soil, the active substance is not detached, as a result of which it has undesirable effects, for example on the existing skin Fauna could develop (bee endangerment by insecticides, which are supposed to prevent the insect infestation of the seed in the soil).

Preparation of the Coating Dispersion The constituents of the coatings described in detail above are generally reacted by first preparing a urea-free, isocyanate-functional prepolymer by reacting components (a), (b), (c) and, if appropriate, (e) Substance ratio of isocyanate groups to isocyanate-reactive groups of the polycarbonate polyol is preferably 0.8 to 4.0, particularly preferably 0.9 to 3.8, in particular 1.0 to 3.5.

In an alternative embodiment, only the component (a) can be reacted separately with the isocyanate (b). Then, then, the addition of components (c) and (e) and their implementation can take place. Subsequently, the remaining isocyanate groups are generally chain-extended or terminated before, during or after dispersion in water, the ratio of isocyanate-reactive groups of the compounds used for chain extension to free isocyanate groups of the prepolymer preferably being between 40 and 150 %, more preferably between 50 to 120%, in particular between 60 to 120%, lies (component (d)). The polyurethane dispersions of the invention are preferably prepared by the so-called acetone process. For the preparation of the polyurethane dispersion by this acetone process, it is usual to use components (a), (c) and (e) which are free of primary or secondary amino groups and polyisocyanate component (b) for the preparation of an isocyanate-functional polyurethane prepolymer. mers wholly or partially and optionally diluted with a water-miscible, but isocyanate-inert solvent and heated to temperatures ranging from 50 to 120 ° C. To accelerate the Isocyanatadditi- onsreaktion known in polyurethane chemistry catalysts can be used, for example dibutyltin dilaurate. Preferably, the synthesis is without a catalyst. Suitable solvents are the usual aliphatic, ketofunctional solvents, e.g. Acetone, butanone, which can be added not only at the beginning of the preparation, but possibly also in parts later. Preferred are acetone and butanone. Other solvents, such as e.g. Xylene, toluene, cyclohexane, butyl acetate, methoxypropyl acetate, solvents with ether or ester units can also be used and distilled off in whole or in part or remain completely in the dispersion.

Subsequently, the optionally not added at the beginning of the reaction components of (c) and (e) are added. In a preferred manner, the prepolymer is prepared without addition of solvent and diluted only for the chain extension with a suitable solvent, preferably acetone.

In the preparation of the polyurethane prepolymer, the molar ratio of isocyanate groups to isocyanate-reactive groups is preferably 0.8 to 4.0, more preferably 0.9 to 3.8, especially 1.0 to 3.5.

The reaction to the prepolymer takes place partially or completely, but preferably completely. Thus, polyurethane prepolymers containing free isocyanate groups are obtained in bulk or in solution.

Subsequently, in a further process step, if not yet done or only partially done, the resulting prepolymer with the aid of aliphatic ketones such as acetone or butanone.

Subsequently, possible NH ₂ , NH-functional and / or OH-functional components are reacted with the remaining isocyanate groups. This chain extension / termination can be carried out either in a solvent before dispersion, during dispersion or in water after dispersion. The chain extension is preferably carried out in water before dispersion.

If compounds corresponding to the definition of (d) with NH ₂ or NH groups are used for chain extension, the chain extension of the prepolymers preferably takes place before the dispersion.

The degree of chain extension, ie the equivalent ratio of NCO-reactive groups of the compounds used for chain extension to free NCO groups of the prepolymer is preferably between 40 and 150%, more preferably between 50 and 120%, in particular between 60 and 120%.

The aminic components (d) can optionally be used individually or in mixtures in water-diluted or solvent-diluted form in the process according to the invention, wherein basically any order of addition is possible.

When water or organic solvents are used as the diluent, the diluent content is preferably 70 to 95% by weight.

The production of the polyurethane dispersion from the prepolymers takes place after the chain extension. For this purpose, the dissolved and chain-extended polyurethane polymer is optionally added either under strong shearing, such as strong stirring, either in the dispersing water or, conversely, the dispersing water is stirred into the prepolymer solutions. Preferably, the water is added to the dissolved prepolymer. The solvent still present in the dispersions after the dispersion step is then usually removed by distillation. A removal already during the dispersion is also possible.

The solids content of the polyurethane dispersion after the synthesis is between 20 to 70 wt .-%, preferably 20 to 65 wt .-%. For coating experiments, these dispersions can be diluted with water as desired 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, such as some 100 nm up to a few 100 microns, which in the context of the present invention also higher and lower thicknesses are possible.

The polyurethane materials for coating the medical devices can be diluted to any desired value by dilution of the aqueous dispersions according to the invention with water. In addition, thickeners can be added in order to increase the viscosity of the polyurethane dispersions optionally. Other additives such as antioxidants, buffering agents to adjust the pH or pigments are also possible. In addition, if desired, further additives such as handle auxiliaries, dyes, matting agents, UV stabilizers, light stabilizers, water repellents, hydrophilizing agents and / or leveling agents may also be used.

On the basis of these dispersions, medical coatings are then produced by the methods described above.

According to the invention, it has been found that the resulting coatings differ on medical devices, depending on whether the coating is produced starting 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 dispersions of the coating compositions described above, since dispersions of the inventive coating systems lead to coatings on the medical devices which have no organic solvent residues, ie toxic are generally harmless, and at the same time lead to a more pronounced hydrophilicity, which can be made for example at a low contact angle. Reference is made to the experiments and comparative experiments explained below.

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

The aqueous polyurethane dispersions used as starting material for the preparation of the coatings can be prepared by any of the methods, but the acetone method described above is preferred.

It can be coated on many substrates such as metals, textiles, ceramics and plastics. Preferably, the coating of medical devices, which are made of metals or plastic. Examples of metals which may be mentioned are: medical stainless steel or nickel-titanium alloys. Medical devices to be coated may consist of various polymeric materials, alone or in combination, such as polyamide, polystyrene, polycarbonate, polyethers, polyesters, polyvinyl acetate, natural and synthetic rubbers, styrene block copolymers 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, further suitable coatings (primers, adhesion promoters) can be applied as a substrate before the application of these hydrophilic coating materials.

In addition to the hydrophilic properties of improving the lubricity, the coatings produced according to the invention are also distinguished 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 coated according to the invention with the hydrophilic polyurethane coatings are demonstrated by comparison 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 Parti cle Sizer (HPPS 3.3) from Malvern Instruments.

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

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 ^® 200 Cl: 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 2000 g / mol (Bayer MaterialScience AG, Leverkusen, DE)

PolyTHF ^v 2000: Polytetramethylenglykolpolyol, 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 ZPropylen- 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 dispersion according to the invention:

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. 71.3 g of 4,4'-bis (isocyanatocyclohexyl) methane were first added to this mixture at 65 ° C. within 1 min (Hi ₂ MDI) and then 11.9 g of isophorone diisocyanate. The mixture was heated to 110 ⁰ C. After 34i 40 min, the theoretical NCO value 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 15 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 having a solids content of 41.5% and an average particle size of 164 nm was obtained.

Example 2:

Preparation of a polyurethaneurea dispersion according to the invention:

269.8 g of Desmophen ^® C 2200, 49.7 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 100.degree. After 21.5 h, the theoretical NCO value was reached. The finished prepolymer was dissolved at 50 ° C in 711 g of acetone and then added at 40 ⁰ 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 41.3% and an average particle size of 109 nm was obtained.

Example 3 Preparation of a Polyurethaneurea Dispersion According to the Invention

277.2 g of Desmophen ^® C 1200, 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.degree. After 2.5 h, the theoretical NCO value was reached. The finished prepolymer was dissolved at 50 ⁰ 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. This gave a storage-stable polyurethane dispersion having a solids content of 40.4% and an average particle size of 146 nm. Example 4:

Preparation of a polyurethaneurea dispersion according to the invention:

282.1 g of Desmophen ^® C 2200, 22.0 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 (H ₁₂ MDI) and then 11.9 g of isophorone diisocyanate. The mixture was heated to 110 ⁰ C. After 21.5 h, the theoretical NCO value 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. Subsequently, the mixture was 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 41.7% and an average particle size of 207 nm was obtained.

Example 5:

Preparation of a polyurethaneurea dispersion according to the invention:

269.8 g of Desmophen ^® XP 2613, 49.7 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 (H ₁₂ MDI) and then 11.9 g of isophorone diisocyanate. The mixture was heated to 110.degree. After 70 minutes, the theoretical NCO value 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 having a solids content of 41.2% and an average particle size of 112 nm was obtained.

Example 6 Preparation of a Polyurethaneurea Dispersion According to the Invention

249.4 g of Desmophen ^® C 2200, 33.1 g of polyether LB 25, 1.9 g of trimethylolpropane 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.degree. After 4 h 20 min, the theoretical NCO value was reached. The finished prepolymer was dissolved at 50 ° C in 720 g of acetone and then added at 40 ° C, a solution of 3.3 g of ethylenediamine in 16 g of water within 10 min. The stirring time was 15 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 having a solids content of 38.9% and an average particle size of 144 nm was obtained.

Example 7:

282.1 g of Desmophen ^® XP 2613, 22.0 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 (H ₁₂ MDI) and then 11.9 g of isophorone diisocyanate. The mixture was heated to 110.degree. After 70 minutes, the theoretical NCO value was reached. The finished prepolymer was dissolved at 50 ⁰ 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 having a solids content of 38.3% and an average particle size of 215 nm was obtained.

Example 8: Preparation of a polyurethane urea dispersion as a comparison product to the inventive example 1. The Desmophen ^® C2200 is replaced by PolyTHF 2000th

277.2 g of polyTHF 2000, 33.1 g of polyether LB 25 and 6.7 g of neopentyl glycol were initially introduced at 65 ° C. and homogenized by stirring for 5 minutes. To this mixture was added at 65 ° C within 1 min, first 71.3 g of 4,4'-bis (isocyanatocyclohexyl) methane (H ₁₂ MDI) and then 11.9 g of isophorone diisocyanate. The mixture was heated to 110.degree. After 18 h, the theoretical NCO value 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 having a solids content of 40.7% and an average particle size of 166 nm was obtained. Example 9:

Preparing a polyurethaneurea dispersion as a comparison product to the inventive example 2. The Desmophen ^® C2200 is exchanged for the PolyTHF 2000th 269.8 g of polyTHF 2000, 49.7 g of polyether LB 25 and 6.7 g of neopentyl glycol were initially introduced at 65 ° C. and homogenized by stirring for 5 minutes. 71.3 g of 4,4'-bis (isocyanatocyclohexyl) methane (H ₁₂ MDI) and then 11.9 g of isophorone diisocyanate were first added to this mixture at 65 ^° C. within 1 minute. The mixture was heated to 100.degree. After 17.5 h, the theoretical NCO value 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 having a solids content of 41.6% and an average particle size of 107 nm was obtained.

Example 10:

Preparation of a polyurethaneurea dispersion as a comparison product to the inventive Example 4. The Desmophen ^® C2200 is replaced by the PolyTHF 2000 off.

282.1 g of polyTHF 2000, 22.0 g of polyether LB 25 and 6.7 g of neopentyl glycol were initially introduced at 65 ° C. and homogenized by stirring for 5 minutes. To this mixture was added at 65 ° C within 1 min, first 71.3 g of 4,4'-bis (isocyanatocyclohexyl) methane (H ₁₂ MDI) and then 11.9 g of isophorone diisocyanate. The mixture was heated to 110.degree. After 21, 5 h the theoretical NCO value 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 having a solids content of 37.5% and an average particle size of 195 nm was obtained.

Example 11: Preparation of Coatings and Measurement of Static

Contact angles 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 on the sample plate of the Clamped spin coater and homogeneously covered with about 2.5 - 3 g aqueous undiluted polyurethane dispersion. By rotating the sample tray for 20 sec at 1300 rpm, a homogeneous coating was obtained, which was dried for 15 min at 100 ° C and then for 24 h at 50 ° C. The resulting coated slides were subjected directly to a contact angle measurement.

From the resulting coatings on the slides, a static contact angle measurement is performed. By means of the video edge angle measuring device OCA20 from Dataphysics with computer-controlled syringes, 10 drops of lipid water are applied to the sample and their static wetting edge angle is measured. Beforehand, the static charge (if present) on the sample surface is removed by means of an antistatic hair dryer.

Table 1: Static contact angle measurements

As Table 1 shows, the polycarbonate-containing coatings of Examples 1 to 7 according to the invention give extremely hydrophilic coatings with static contact angles <45 °. The coatings of Examples 1 to 6 give extraordinarily hydrophilic coatings with static contact angles <30 °. In contrast, the polyTHF-containing coatings from Comparative Examples 7 to 10 are substantially more unpopular, although the composition of these coatings is otherwise identical to those of Examples 1, 2 and 4. In addition, data disclosed in "Evaluation of a poly (vinylpyrollidone) -coated bio-material for urological use", MM Tanney, SP Gorman, Biomaterials 23 (2002), 4601-4608, show that the contact angles of polyurethane at about 97 ° and of PVP-coated polyurethane at about 50 °.

Example 12: Measurement of coagulation parameters

From the polyurethane dispersion of Example 1, a film for blood contact studies was prepared by spincoating on glass. The sample surface was placed in an autoclaved incubation chamber and incubated with 1.95 ml of blood. The exact experimental setup is described in U. Streller et al. J. Biomed. Mater. Res B, 2003, 66B, 379-390.

The venous blood needed for the trial was taken via a 19 G cannula to a male donor who had not taken any medication for at least 10 days. Coagulation was prevented by addition of heparin (2 iU / ml). The thus prepared blood was then filled into the incubation chamber equipped with the polyurethane surface, preheated to 37 ° C., and incubated for 2 h at 37 ° C. with permanent rotation of the chamber. As comparative materials, glass and polytetrafluoroethylene (PTFE) were used. Glass is a strong activating surface for blood clotting, while PTFE is a polymer which is an acceptable material for many applications (see U. Streller et al., J. Biomed., Mater., Res B, 2003, 66B, 379-390).

After incubation, three parameters were measured:

Thrombin-antithrombin complex (Enzygnost TAT micro, Dade Behring GmbH, Marburg, Germany)

Platelet factor 4 (ELIS A PF 4 complete kit from Haemochrom Diagnostica GmbH, Essen, Germany)

The platelet reduction was measured in EDTA-anticoagulated blood by means of an automatic cell counting system (AcTdiff from Coulter, Krefeld, Germany).

Table 2: thrombin-antithrombin complex

Table 3: Platelet Factor 4

Table 4: Platelet reduction in the blood

All three measured blood parameters show that the hydrophilic polyurethane of Example 1 activates coagulation only to a very moderate degree. The thrombin-antithrombin complex as a measure of the activation of the intrinsic coagulation cascade shows that the polyurethane itself produces lower values compared to the PTFE, which is considered to be very blood-compatible, and thus causes even lower activation.

Platelet factor 4 is a marker for platelet activation. Also, this cellular part of the coagulation is activated only slightly by the hydrophilic polyurethane. The good blood compatible PTFE causes a higher activation. Also, the reduction of platelets is clear for glass and PTFE, which means that a part of the platelets attach to these surfaces. In contrast, the hydrophilic polyurethane of Example 1 is virtually no waste to recognize.

Example 13:

Synthesis of an aqueous dispersion with terminal polyethylene oxide building blocks as comparison material to the inventive examples, in which a polyurethane is used, which is terminated by a copolymer of polyethylene oxide and polypropylene oxide. The polyether LB 25 used in the context of the present invention is replaced in this example by equal molar amounts of a comparable pure polyethylene oxide ether. 277.2 g of Desmophen ^® C 2200, 29.4 g of polyethylene glycol 2000 monomethyl ether (Source:. Fluka, CAS No. 9004-74-4) 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 (Hj ₂ MDI) and then 11.9 g of isophorone diisocyanate. The mixture was heated to 110.degree. After 35 minutes, the theoretical NCO value 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. The removal of the solvent followed by distillation in vacuo. A storage-stable polyurethane dispersion having a solids content of 40.0% and an average particle size of 130 nm was obtained.

As described in Example 11, a coating on glass was prepared by spin coating and the static contact angle of this coating was determined. This gave a static contact angle of 45 °. The comparison of this value with the value for the coating of Example 1 (<10 °, see Table 1 in Example 11) shows that the use of the mixed polyethylene oxide polypropylene monoxide LB 25 compared to pure polyethylene oxide monool significantly lower contact angles and thus more hydrophilic Coatings possible.

Example 14:

Synthesis of the polyurethaneurea polymer of Inventive Example 1 as Comparative Example in Organic Solution. and a mixture of 277.2 g of Desmophen ^® C 2200, 33.1 g LB 25, 6.7 g of neopentyl glycol at 60 ° C 71.3 g of 4,4'-bis (isocyanatocyclohexyl) methane (H ₁₂ MDI) and Added 11.9 g of isophorone diisocyanate. The mixture was heated to 110 ° C and continued to a constant NCO content of 2.4 microns. The mixture was allowed to cool and diluted with 475 g of toluene and 320 g of isopropanol. At room temperature, a solution of 4.8 g of ethylenediamine in 150 g of 1-methoxy-2-propanol was added inside. After complete addition, stirring was continued for 2 h. This gave 1350 g of a 30.2% strength polyurethane urea solution in toluene / isopropanol / 1-methoxypropanol-2 having a viscosity of 607 mPas at 23 ° C.

As described in Example 11, a coating on glass was prepared by spin coating and the static contact angle of this coating was determined. A static contact angle of 27 ° was determined. The comparison of this value with the value for the coating of Example 1 (<10 °, see Table 1 in Example 11), a structurally the same coating, but dispersed in water, shows that the coatings from aqueous dispersion compared to coating, which are obtained starting from corresponding solutions, yield more hydrophilic coatings.

Claims

Claims:

Use of a coating composition in the form of a dispersion comprising a polyurethaneurea which (1) is terminated with a copolymer unit of polyethylene oxide and polypropylene oxide, and

(2) at least one hydroxyl group-containing polycarbonate polyol. for coating substrates.

2. Use according to claim 1, characterized in that the polyurethaneurea has units which are based on at least one aliphatic, cycloaliphatic or aromatic isocyanate.

3. Use according to claim 1 or 2, characterized in that the polyurethane urethane has a maximum ionic modification of 2.5 wt .-%.

4. Use according to one of claims 1 to 3, characterized in that the coating comprises a polyurethaneurea which is composed of 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 bis

2,3 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 4.0 mol per mole of the polycarbonate polyol; c) at least one monofunctional mixed polyoxyalkylene ether of polyethylene oxide and polypropylene oxide 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 amino alcohol as a so-called chain extender or mixtures of such compounds in an amount of from 0.05 to 3.0 mol per mol 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 0.1 to 1.0 mol; and optionally amine- or OH-containing building blocks which are located at the polymer chain ends and terminate.

5. Use according to any one of claims 1 to 4, comprising the steps

A) Preparation of a coating composition by

(I) presentation of components (a), (b), (c) and optionally (e) as defined in claim 4 and optionally diluted with a water-miscible but isocyanate-inert solvent;

(II) heating the composition obtainable from (I) to temperatures in the range from 50 to 120 ° C; (HI) metering in the components of (c) and (e) which may have not yet been added at the beginning of the reaction;

(IV) dissolving the resulting prepolymer with the aid of aliphatic ketones;

(V) addition of the component (d) for chain extension; (VI) adding water for dispersion; and

(VIT) removal of the aliphatic ketone, preferably by distillation and

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

6. Use according to one of claims 1 to 6 for the coating of at least one medical device.

7. Use according to one of claims 1 to 6 for the coating of technical substrates in the non-medical field.

8. Use according to one of claims 1 to 6 for the production of easy-to-clean or self-cleaning surfaces.

9. Use according to one of claims 1 to 6 for the coating of glazings and optical glasses and lenses.

10. Use according to one of claims 1 to 6 for the coating of substrates in the sanitary sector.

11. Use according to one of claims 1 to 6 for coating packaging materials.

12. Use according to any one of claims 1 to 6 for reducing the growth of the coated surfaces.

13. Use according to one of claims 1 to 6 for the coating of over- and underwater substrates for reducing the frictional resistance of the substrates to water.

14. Use according to one of claims 1 to 6 for printing preparation of substrates.

15. Use according to one of claims 1 to 6 for the preparation of formulations for cosmetic applications.

16. Use according to one of claims 1 to 6 for the production of active substance release systems for coating seeds.