KR20110090967A - Composition containing antimicrobials in a hybrid network - Google Patents

Abstract

The present invention has (a) an isocyanate component containing on average two or more isocyanate groups per molecule and (B) an average of two or more functional groups reactive per isocyanate per molecule, and at least one alkoxysilane ( Reacting the binder component comprising B2) to obtain a prepolymer, followed by (b) at least one antimicrobial agent (Z) comprising water and at least one antimicrobial active material (Z1) and optionally a particulate carrier material (Z2). Hydrolyzing and polycondensing the prepolymer in the presence of a), wherein the at least one antimicrobial active substance (Z1) is non-reactive during step (b). The invention also relates to a kit comprising a composition obtainable by the above method, a coating comprising said composition and a curable composition containing said components (A), (B) and (Z) for application of the joints. . The invention also relates to the use of said composition for the production of antimicrobial coatings.

Description

COMPOSITION CONTAINING ANTIMICROBIALS IN A HYBRID NETWORK}

The present invention

(a)-(A) an isocyanate component containing two or more isocyanate groups on average per molecule

(B) a binder component having, on average, at least two functional groups reactive to isocyanates and comprising at least one alkoxysilane (B2)

To react to obtain a prepolymer, and then

(b)-water and

At least one antimicrobial agent (Z) comprising at least one antimicrobial active material (Z1) and optionally a particulate carrier material (Z2)

Hydrolyzing and polycondensing said prepolymer in the presence of, wherein at least one antimicrobial active agent (Z1) is non-reactive during step (b).

The invention also relates to a kit comprising a composition obtainable by the above method, a coating comprising said composition and a curable composition containing said components (A), (B) and (Z) for application of the joints. . The invention also relates to the use of said composition for the production of antimicrobial coatings.

Coating applications are becoming increasingly demanding in terms of performance, stability and environmental compliance. Coatings based on isocyanates and binders, ie components containing hydrogen atoms reactive towards isocyanates (hereinafter referred to as polyurethane coatings) are known to provide high chemical resistance, flexibility, abrasion resistance, weather resistance and impact resistance. It is. The protection provided by such coatings is of particular importance in the automotive, construction, marine and chemical sectors.

The polyurethane coating or film can be produced, for example, by reacting a polyfunctional hydroxyl group or amino group-containing compound (polyol or polyamine) with a polyfunctional isocyanate (polyisocyanate) in an isocyanate addition polymerization process. The reaction between the isocyanate group (NCO) and the active hydrogen atoms of the binder is mainly promoted by the catalyst.

Generally one-component (1K) coating material and two-component (2K) coating material can be distinguished. Two-component coating materials do not mix until just before application and therefore have only a limited process time. This type of system is characterized by rapid curing after the components are mixed. In contrast, one-component systems have a long pot life (ie, a length of time for which the catalyzed resin system maintains a viscosity low enough to be used for processing). This has been achieved to date by, for example, blocking NCO groups. However, when this coating cures, the blocking agent comes out.

It is well known in the art that two-component curable mixtures comprising polyisocyanates and binders, in particular binders based on polyols or polyamines, provide excellent performance and curing at low temperatures.

There is a need in the art to develop coatings with long term antimicrobial properties in parallel with the above-mentioned advantages. As a result, several different coatings have been proposed in the prior art.

The use of aluminosilicates or zeolites containing ions of certain metals is known, for example, from US Pat. No. 452,410 and US Pat. No. 5,556,699. However, coatings comprising zeolites or aluminosilicates are not transparent and their use is often limited to coatings less than 15 microns thick.

The use of compositions comprising silane copolymers and antibacterial agents wherein the copolymer is a reaction product of one or more polyisocyanates, organo-functional silanes and polyols is known from US Pat. No. 6,596,401. However, US Pat. No. 6,596,401 does not disclose a hybrid network.

US Pat. No. 6,572,926 discloses polymer substrates that are exposed to a polymerizable quaternary ammonium salt, such as dimethyloctadecyl- [3- (trimethoxysilyl) propyl] ammonium chloride, dissolved in a solvent. The quaternary salt in the solvent is adsorbed onto the polymer substrate and polymerized, whereby the substrate is impregnated with an antimicrobial agent on its surface. The polymerized agent also penetrates the surface to a certain depth to form an interpenetrating network.

The method is limited to penetration or swelling of the polymer substrate by a particular mixture of polymerizable quaternary ammonium salts and solvents. In another embodiment it is disclosed to add a polymeric quaternary ammonium salt to a commercially available coating so that the interpenetrating network forms in situ. Nevertheless, leaching from the coating can only be avoided by polymerizing the antimicrobial agent. In addition, the disclosed coatings still do not exhibit sufficient antimicrobial activity against E. coli.

It is an object of the present invention to provide an antimicrobial composition in which the antimicrobial actives are not leached from the composition. A related object of the present invention is to provide a coating with long lasting antimicrobial activity, in particular weather resistance and lasting for 5 years. Antimicrobial coatings should be available for a wide range of antimicrobials.

Another object of the present invention is to provide an antimicrobial composition, in particular a coating, which shows high efficacy against Staphylococcus aureus and E. coli. In addition, the antimicrobial coating must efficiently kill these bacteria within a period of 24 hours or less at room temperature.

At the same time it is an object of the present invention to provide an antimicrobial coating which is chemical and weather resistant and exhibits high optical quality, sufficient flame retardancy, good adhesion to polycarbonate and aluminum substrates and high wear resistance.

The problems mentioned previously are solved by the process of the invention and the compositions and coatings obtainable by the process. Preferred embodiments are outlined below and in the claims. Combinations of preferred embodiments are within the scope of the present invention.

The process of the invention for preparing the composition comprises steps (a) and (b) as defined above. Steps (a) and (b) are outlined in more detail below. It is preferred if the composition according to the invention is present as a coating.

step  (a)

According to the invention, step (a)

(A) an isocyanate component containing at least two isocyanate groups on average per molecule;

(B) a binder component having, on average, at least two functional groups reactive to isocyanates and comprising at least one alkoxysilane (B2)

Reacting to obtain a prepolymer.

Prepolymers are referred to as polymer systems that still contain reactive groups or reactive moieties that can be further polymerized and / or crosslinked. In the present case, the alkoxysilane (B2) contains a hydrolyzable group which forms an inorganic network as part of the hybrid network produced in the presence of water according to step (b).

Each mean value referring to a sensory value refers to a number-weighted mean.

The molar ratio of NCO groups and reactive functional groups in component (A), ie reactive hydrogen atoms in component (B), may vary relatively broadly. The molar ratio of the NCO group in (A): reactive hydrogen atom in (B) may be 10: 1 to 1:10. However, it is preferable that the molar ratio of the reactive hydrogen atoms in the NCO group: (B) in (A) is 2: 1 to 1: 2, especially 1.1: 0.9 to 0.9: 1.1. It is especially preferable that the molar ratio of the NCO group in (A): reactive hydrogen atom in (B) is substantially 1: 1.

Isocyanate Component (A)

Isocyanates suitable for the present invention are known to those skilled in the art or may be synthesized according to methods known to those skilled in the art.

The term isocyanate refers to a molecule containing one or more -NCO groups per molecule. The isocyanate component may consist of a single isocyanate containing at least two -NCO groups per molecule or a mixture of different isocyanates containing at least two -NCO groups on average per molecule. The isocyanate component (A) according to the invention thus has a number average functionality of at least two —NCO groups. The term diisocyanate refers to isocyanate compounds containing two -NCO groups per molecule.

Component (A) preferably contains at least one oligomer based on at least one diisocyanate having more than two NCO-functional groups, referred to below as polyisocyanates. Such diisocyanate based oligomers have units derived from diisocyanates and have oligomer structures known to those skilled in the art. Preferably, component (A) is oligomeric diphenylmethane diisocyanate (oligomeric MDI) known to the person skilled in the art as PMDI or raw MDI.

As parent diisocyanate, diisocyanates having 4 to 20 carbon atoms are preferably used. In principle, the parent diisocyanates can be used on their own or as a mixture with oligomers. However, diisocyanates are preferably used in oligomeric form.

Examples of typical diisocyanates include aliphatic diisocyanates such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate Isocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate; Derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate; Alicyclic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1 Isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1,3- or 1,4-bis (isocyanatomethyl) cyclo Hexane or 2,4- or 2,6-diisocyanato-1-methylcyclohexane, and 3 (or 4), 8 (or 9) -bis (isocyanatomethyl) tricyclo [5.2.1.02, 6] decane isomer mixtures and aromatic diisocyanates such as toluene 2,4- or 2,6-diisocyanate and isomer mixtures thereof, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-di Socianate diphenylmethane and isomer mixtures thereof, phenylene 1,3- or 1,4-diisocyanate, 1-chlorophenylene 2,4-diisocyanate, naphthylene 1,5-diisocyanate, bi Nylene 4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 3-methyldiphenylmethane 4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1 , 4-diisocyanatobenzene or 4,4'-diisocyanatodiphenyl ether.

Also suitable are in principle higher isocyanates having an average of more than two isocyanate groups. Suitable examples include triisocyanates such as triisocyanatononane, 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4'-triisocyanato-diphenyl ether, or corresponding Mixtures of diisocyanates, triisocyanates and higher polyisocyanates which are obtained by phosgenating aniline / formaldehyde condensates and represent polyphenyl polyisocyanates containing methylene crosslinking are included.

Alicyclic and aliphatic diisocyanates are preferred. 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) -cyclohexane (isophorone diisocyanate), 1,6-diisocyanatohexane, 4,4'-di Particular preference is given to (isocyanatocyclohexyl) methane and 3 (or 4), 8 (or 9) -bis (isocyanatomethyl) tricyclo [5.2.1.02,6] decane isomer mixtures.

Component (A) comprises polyisocyanate and polyisocyanate-containing mixtures containing biuret, urethane, allophanate and / or isocyanurate groups, preferably polyisocyanate and / or allophanate groups containing isocyanurate groups It may contain a polyisocyanate containing. Particular preference is given to polyisocyanates which mainly contain isocyanurate groups. It is very particularly preferred that the fraction of the isocyanurate groups corresponds to an NCO value of at least 5% by weight, preferably at least 10% by weight and more preferably at least 15% by weight (C ₃ N _{3 with a} molar mass of 126 g / mol). Calculated as O ₃ ).

Examples of preferred polyisocyanates as component (A) include the following:

1) Polyisocyanates having isocyanurate groups and obtained from aromatic, aliphatic and / or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanatoisocyanurates, in particular hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present are in particular trisisocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates which are cyclic trimers of diisocyanates or mixtures with their higher homologs having more than one isocyanurate ring. . Isocyanatoisocyanurates generally have an NCO content of 10 to 30% by weight, in particular 15 to 25% by weight, and an average NCO functionality of 2.6 to 8.

2) uretdione diisocyanates, especially hexamethylene diisocyanate or iso, having aromatic, aliphatic and / or cycloaliphatic bonded isocyanate groups, preferably aliphatic and / or cycloaliphatic bonded groups Uretdione diisocyanate derived from phorone diisocyanate. Uretdione diisocyanate is a cyclic dimerization product of diisocyanate. Uretdione diisocyanates can be used as single component or as a mixture with other polyisocyanates, especially those mentioned in 1).

3) polyisocyanates, in particular tris (6-isocyanatohexyl) burette, having a buret group and having an aromatic, cycloaliphatic or aliphatic bonded, preferably cycloaliphatic or aliphatic bonded isocyanate group; Mixtures with their higher homologs. Such polyisocyanates with biuret groups generally have an NCO content of 18 to 22% by weight and an average NCO functionality of 2.8 to 6.

4) an isocyanate group having an urethane and / or allophanate group and having an aromatic, aliphatic or cycloaliphatic bonded, preferably aliphatic or cycloaliphatic bonded, e.g. excess hexamethylene diisocyanate Or excess isophorone diisocyanate and monohydric or polyhydric alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol, n-pentanol, stearyl alcohol, cetyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, 1,3-propanediol monomethyl ether, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, trimethylolpropane, neopentyl glycol, pentaerythritol, 1,4-butanediol, 1,6-hexanediol, 1,3-propanediol, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, ethylene glycol, diethylene glycol, tri Ethylene glycol, tetraethylene glycol, pentaethylene glycol, glycerol, 1,2-dihydroxypropane, 2,2-dimethyl-1,2-ethanediol, 1,2-butanediol, 1,4-butanediol, 3-methyl Pentane-1,5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyl-octane-1,3-diol, neopentyl glycol hydroxypivalate, ditrimethylolpropane, dipentaerytate Ritol, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol, 1,2-, 1,3- Or polyisocyanates obtainable by reaction with 1,4-cyclohexanediol or mixtures thereof. Such polyisocyanates with urethane and / or allophanate groups generally have an NCO content of 12 to 24% by weight, in particular 18 to 24% by weight and an average NCO functionality of 2.5 to 4.5, based on HDI.

5) Polyisocyanates comprising oxadiazinetrione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such polyisocyanates comprising oxadiazinetrione groups can be prepared from diisocyanates and carbon dioxide.

6) Polyisocyanates comprising iminooxadiazinedione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such polyisocyanates comprising iminooxadiazinedione groups can be prepared from diisocyanates using specific catalysts.

7) uretonimine-modified polyisocyanates.

8) carbodiimide-modified polyisocyanates.

9) Superbranched polyisocyanates of the type known for example from DE-A1 10013186 or DE-A1 10013187.

10) Polyurethane polyisocyanate prepolymers from di- and / or polyisocyanates with alcohols.

11) polyurea-polyisocyanate prepolymers.

Polyisocyanates 1) to 11) can be used as mixtures, where appropriate also as mixtures with diisocyanates.

Preference is given to polyisocyanates containing isocyanurates and / or biuret groups. In addition, such mixtures may also contain small amounts of uretdione, biuret, urethane, allophanate, oxadiazinetrione, iminooxadiazinedione and / or uretonimine groups, preferably in each case 25 Less than 20% by weight, more preferably less than 20% in each case, very preferably less than 15% in each case, in particular less than 10% in each case, in particular less than 5% in each case, very particularly less than 2% in each case It may contain.

Having an NCO content of 16.7% to 17.6% (according to DIN EN ISO 11909) as an isocyanate in component (A) and / or an average NCO functionality of 3.0 to 4.0, preferably 3.0 to 3.7, more preferably 3.1 to 3.5 Especially preferred isocyanurate of isophorone diisocyanate. Compounds of this type containing isocyanurate groups preferably have a HAZEN / APHA color number of 150 or less according to DIN EN 1557.

In addition, the NCO content of 21.5 to 23.5% (according to DIN EN ISO 11909) and / or 3.0 to 8, preferably 3.0 to 3.7, more preferably 3.1 to 3.5, as isocyanate in component (A) Particularly preferred isocyanurate of 1,6-hexamethylene diisocyanate having. Compounds of this type containing isocyanurate groups preferably have a color number of 60 or less according to DIN ISO 6271. Compounds of this type containing isocyanurate groups preferably have a viscosity of 1000 to 20000 mPas, preferably 1000 to 4000 mPas, at 23 ° C. at a shear rate of 1000 s ⁻¹ , according to DIN EN ISO 3219.

In one preferred embodiment the isocyanate component (A) has a total chlorine content of less than 400 mg / kg, more preferably less than 80 mg / kg, very preferably less than 60 mg / kg, in particular less than 40 mg / kg, in particular less than 20 mg / kg, It even has a total chlorine content of less than 10 mg / kg.

Isocyanate component (A) is 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) -cyclohexane (isophorone diisocyanate), 1,6-diisocyanatohexane ( HDI), 4,4'-di (isocyanatocyclohexyl) methane, and 3 (or 4), 8 (or 9) -bis (isocyanatomethyl) -tricyclodecane and isomer mixtures thereof It is particularly preferable to contain one or more compounds.

Very particular preference is given to 1,6-diisocyanatohexane (HDI).

Binder Component (B)

According to the invention, the binder component (B) comprises at least one alkoxysilane (B2), the binder component (B) having on average two or more functional groups per molecule reactive to isocyanates.

In a preferred embodiment, the binder component (B) comprises at least one binder (B1) which cannot react in step (b), and at least one alkoxysilane (B2).

Preferably, the binder (B1) which cannot react in step (b) is a binder having no alkoxysilane group.

Binders (B1) suitable for the present invention are known to those skilled in the art or can be synthesized according to methods known to those skilled in the art.

The binder (B1) for the purposes of the present invention is preferably a compound containing at least two hydrogen atoms reactive towards isocyanates. In particular, the binder contains hydroxyl groups (OH groups) and / or primary and / or secondary amino groups.

In one embodiment of the invention, polyols or polyamines are used as binder (B1). Polyols are referred to as organic molecules comprising an (number-weighted) average number of two or more OH groups per molecule. Polyamines are also referred to as organic molecules comprising an (water-weighted) average number of at least two primary or secondary (ie reactive) amino groups per molecule.

Component (B) preferably exhibits an OH number of at least 15 mg KOH, preferably at least 40 mg KOH, more preferably at least 60 mg KOH, very preferably at least 80 mg KOH per g of resin solid according to DIN 53240-2. The OH number can be 350 mg KOH or less, preferably 240 mg KOH or less, more preferably 180 mg KOH or less, very preferably 140 mg KOH or less per g solid resin.

Preferred OH numbers also depend on the field of application. Manfred Bock, “Polyurethane fuer Lacke und Beschichtungen”, p. 80, Vincentz-Verlag, 1999], low OH numbers are advantageous for effective adhesion and corrosion control. For topcoat materials, for example, polyacrylates having an OH number of about 40 to 100 mg KOH per gram of resin solid are used; Weather resistant coating materials include materials having an OH number of about 135 mg KOH; And for high chemical resistance, a material having an OH number of about 170 mg KOH is used. Polyesters for aircraft coatings have even higher OH numbers in some cases.

Preferably, the binder component (B) contains at least one polyol or at least one polyamine or both, at least one polyol and at least one polyamine as binder (B1). Particular preference is given to binder components (B1) containing at least one polyol.

Examples of preferred binders (B1) include polyacrylate polyols, polyester polyols, polyether polyols, polyurethane polyols; Polyurea polyols; Polyester polyacrylate polyols; Polyester polyurethane polyols; Polyurethane polyacrylate polyols, polyurethane modified alkyd resins; Fatty acid modified polyester polyurethane polyols, copolymers with allyl ethers, for example graft polymers of the specified group of compounds having different glass transition temperatures and also mixtures of the specified binders. Polyacrylate polyols, polyester polyols and polyether polyols are particularly preferred, in particular at least 2, preferably 2 to 10, more preferably 3 to 10 and very preferably 3 to 8 averages per molecule Preference is given to one or more polyacrylate polyols containing hydroxyl groups.

The preferred OH value of the preferred binder (B1) measured according to DIN 53240-2 is 40 to 350 mg KOH, preferably 80 to 180 mg KOH, per g of resin solids in polyester, and per g of resin solids in polyacrylate-ol. 15 to 250 mg KOH, preferably 80 to 160 mg KOH.

The binder (B1) may additionally have an acid value of 200 mg KOH / g or less, preferably 150 mg KOH / g or less, more preferably 100 mg KOH / g or less according to DIN EN ISO 3682.

The acid value of the binder (B1) should preferably be at least 10 mg KOH / g, more preferably at least 80 mg KOH / g. Alternatively, it may be less than 10 mg KOH / g so that the binder is virtually free of acid.

Polyacrylate polyols of this type preferably have a molecular weight Mn of at least 1000 g / mol, more preferably at least 2000 g / mol and very preferably at least 5000 g / mol. The molecular weight Mn can be, for example, 200000 g / mol or less, preferably 100000 g / mol or less, more preferably 80000 g / mol or less, very preferably 50000 g / mol or less.

The polyacrylate polyol is an air of at least one (meth) acrylic acid ester and at least one compound having at least one, preferably exactly one hydroxy group and at least one, preferably exactly one (meth) acrylate group It is coalescing.

The latter are, for example, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid (abbreviated herein as "(meth) acrylic acid") and preferably 2 to 20 C atoms and at least two hydroxyl groups Diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2-ethanediol, dipropylene glycol, tri Ethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, neopentyl glycol hydroxypivalate, 2-ethyl-1,3-propanediol , 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, 2-ethyl-1 , 4-butanediol, 2-ethyl-1,3-hexanediol, 2,4-diethyl-octane-1,3-diol, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1- , 1,2-, 1,3- And 1,4-bis (hydroxymethyl) cyclohexane, 1,2-, 1,3- or 1,4-cyclohexanediol, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, Ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, trytol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulitol (galactitol), Maltitol, isomalt, poly-THF, poly-1,3-propanediol having a molar weight of 162 to 4500, preferably 250 to 2000 or polypropylene glycol having a molar weight of 134 to 2000 or a molar weight of 238 to 2000 Monoesters of polyethylene glycol.

2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1,4-butanediol monoacrylate or 3- (acryloyloxy) -2-hydroxy Propyl acrylate is preferred, with 2-hydroxyethyl acrylate and / or 2-hydroxyethyl methacrylate being particularly preferred.

The hydroxyl-comprising monomer is another polymerizable monomer, preferably a free-radically polymerizable monomer, preferably more than 50% by weight of C ₁ -C ₂₀ , preferably C ₁ -C ₄ Alkyl (meth) acrylates, (meth) acrylic acid, vinylaromatics with up to 20 C atoms, vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl halides, 4 to 8 C atoms and 1 Or as a mixture with a monomer consisting of a non-aromatic hydrocarbon having two double bonds, an unsaturated nitrile and a mixture thereof. Particular preference is given to polymers consisting of more than 60% by weight of C ₁ -C ₁₀ alkyl (meth) acrylates, styrene, vinylimidazole or mixtures thereof.

Said polymers are hydroxy-functional monomers according to the hydroxy group content, if appropriate further monomers, for example (meth) acrylic acid glycidyl epoxy esters, ethylenically unsaturated acids, especially carboxylic acids, acid anhydrides or acid amides. It may include.

Further polymers are, for example, polyesterols obtainable by condensation of polycarboxylic acids, in particular dicarboxylic acids with polyols, in particular diols. In order to ensure suitable polyester polyol functionality for the polymerization, some triols, tetrol and the like, and also triacids and the like are also used.

Polyester polyols are described, for example, in Ullmanns Enzyklopaedie der technischen Chemie, 4th edition, volume 19, pp. 62 to 65. Preference is given to using polyester polyols obtained by reacting dihydric alcohols with dibasic carboxylic acids. It is also possible to use the corresponding polycarboxylic acid anhydrides or the corresponding polycarboxylic esters of lower alcohols or mixtures thereof in place of the free polycarboxylic acids to prepare the polyester polyols. The polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic, and if appropriate may be substituted with halogen atoms and / or may be unsaturated, for example. Examples that may be mentioned include:

Oxalic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanediic acid, o-phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid Or tetrahydrophthalic acid, suveric acid, azelaic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, dimer fatty acid, Isomers and hydrogenation products thereof, and also esterifiable derivatives such as anhydrides or dialkyl esters, C ₁ -C ₄ alkyl esters of the specified acids, for example methyl, ethyl or n-butyl esters, are used. Dicarboxylic acids of the formula HOOC- (CH ₂ ) _y -COOH, wherein y is a number from 1 to 20, preferably even from 2 to 20, preferably succinic acid, adipic acid, sebacic acid and Dodecanedicarboxylic acid is preferred.

Suitable polyhydric alcohols for the production of polyesterols include 1,2-propanediol, ethylene glycol, 2,2-dimethyl-1,2-ethanediol, 1,3, which may be alkoxylated as described above as appropriate. Propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyl Octane-1,3-diol, 1,6-hexanediol, poly-THF having a molar mass of 162 to 4500, preferably 250 to 2000, poly-1,3-propanediol having a molar mass of 134 to 1178 , Poly-1,2-propanediol having a molar mass of 134 to 898, polyethylene glycol having a molar mass of 106 to 458, neopentyl glycol, neopentyl glycol hydroxypivalate, 2-ethyl-1,3-propane Diol, 2-methyl-1,3-propanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedi Methanol, 1,2-, 1,3- or 1,4-cyclohexanediol, trimethylolbutane, trimes Olpropane, trimethylolethane, neopentyl glycol, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, trytol, erythritol, adonitol (ribitol), arabitol (Rixitol), xylitol, dulcitol (galactitol), maltitol or isomalt.

Preferred alcohols are alcohols of the formula HO- (CH ₂ ) _X -OH wherein x is a number from 1 to 20, preferably even from 2 to 20. Preferred are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. Neopentyl glycol is additionally preferred.

Also suitable are polycarbonate diols of the type obtainable by reacting, for example, excess low molecular weight alcohols specified as synthetic components for phosgene and polyester polyols.

Also suitable are lactone-based polyester diols which are homopolymers or copolymers of lactones, preferably hydroxy-terminated adducts of lactones with suitable difunctional starting molecules. Suitable lactones are preferably of the formula HO- (CH ₂ ) _Z -COOH, wherein z is a number from 1 to 20, and one H atom of the methylene unit can also be substituted with a C ₁ to C ₄ alkyl radical Derived from the compound). Examples include ε-caprolactone, β-propiolactone, gamma-butyrolactone and / or methyl-ε-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone and their Mixture. Examples of suitable starting components include the low molecular weight dihydric alcohols specified above as synthetic components for the polyester polyols. Particular preference is given to corresponding polymers of ε-caprolactone. Lower polyester diols or polyether diols can also be used as starting materials for the production of lactone polymers. Instead of the polymers of lactones, it is also possible to use chemically equivalent corresponding polycondensates of the hydroxycarboxylic acids corresponding to the lactones.

Also suitable as polymers are polyetherols prepared by the addition reaction of ethylene oxide, propylene oxide or butylene oxide with the H-active component. Also suitable are polycondensates of butanediol. In addition, hydroxy-functional carboxylic acids such as, for example, dimethylolpropionic acid or dimethylolbutanoic acid can be used.

In addition, the polymer may naturally be a compound containing primary or secondary amino groups.

Preferably, the binder (B1) is a polyol and / or a polyamine, in particular polypropylene glycol or 1,5-pentanediol.

Alkoxysilane  (B2)

According to the invention, step (a) comprises reacting an isocyanate component (A) and a binder component (B), wherein the binder component (B) comprises at least one alkoxysilane and is average on 2 reactive to isocyanates Has more than one functional group.

Preference is given to alkoxysilanes (B2) having two reactive functional groups per molecule. The functional group is preferably a hydroxyl group or a primary or secondary amino group which is reactive toward isocyanate. Particular preference is given to alkoxysilanes (B2) having two primary and / or secondary amino groups.

 In a particularly preferred embodiment, the alkoxysilane (B2) comprises at least one compound according to formula (I), wherein the alkoxysilane (B2) contains two or more functional groups reactive to isocyanates.

<Formula I>

Where

n is an integer from 1 to 6;

R ¹ is selected from H and a C ₁ -C ₆ alkyl group which may be linear, branched or cyclic;

R ² and R ³ are independently selected from OH, OR ¹ , and C ₁ -C ₆ alkyl groups which may be linear, branched or cyclic, wherein R ¹ has the meanings indicated above;

R ⁴ and R ⁵ are independently selected from C ₁ -C ₆ alkyl groups, C ₁ -C ₆ aminoalkyl, and C ₁ -C ₆ hydroxyalkyl, which may be H, linear, branched or cyclic, wherein said alkyl group Linear, branched or cyclic.

-CH ₂ CH ₂ -NH ₂ and -CH ₂ CH ₂ -OH are particularly preferred as R ⁴ and R ⁵ .

Alkoxysilane (B2) is N- (3- (trimethoxysilyl) propyl) ethylene diamine, 1- (3- (trimethoxysilyl) propyl) diethylene triamine, bis (3- (methylamino) propyl) Trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl dimethoxysilane, γ-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyl trimethoxysilane, N-phenyl aminomethyl triethoxy silane and bis- (γ-trimethoxysilyl propyl) amine and a combination of the above alkoxysilanes Very particular preference is given to cases selected from one or more.

Selecting an alkoxysilane (B2) from one or more of the group consisting of 3- [bis (2-hydroxyethyl) amino] propyl triethoxysilane] and 3- (2-aminoethylamino) propyl) trimethoxysilane Even more preferred.

The alkoxysilane compound (B2) is preferably present in the range of 2 to 60% by weight, based on the total weight of components A and B. Particular preference is given if the alkoxysilane compound (B2) is present in an amount of from 6 to 30% by weight, based on the total weight of components A and B, very particularly preferably from 10 to 20% by weight.

The reaction of the compounds according to the invention can be carried out in several variants. In one embodiment, the isocyanate component (A) is reacted simultaneously with the total amount of binder components (B1) and (B2).

In another embodiment, the binder component (B1) is reacted with excess diisocyanate to form an isocyanate-capped polyurethane prepolymer. The formation of such prepolymers can be facilitated by using an excess of isocyanate component (A). That is, the number of isocyanate functional groups present in the reaction mixture exceeds the number of alcohol functional groups present in the reaction mixture. Preferably, the ratio of isocyanate functional groups to alcohol or other isocyanate-reactive functional groups is from 1.1: 1 to 2: 1. More preferably, the ratio of isocyanate functional group to alcohol functional group is 1.5: 1 to 2: 1, most preferably 1.6 to 1.8.

The isocyanate-capped polyurethane prepolymer is then reacted with an alkoxysilane (B2) to form a polyurethane-urea-siloxane copolymer having pendant alkoxy groups.

Step (b)

According to step (b) of the present invention, the prepolymer obtained in step (a)

-Water and

At least one antimicrobial agent (Z) comprising at least one antimicrobial active substance (Z1) and optionally a particulate carrier material (Z2) which is non-reactive during step (b).

Hydrolysis and polycondensation in the presence of.

The term "antibacterial active material" denotes a compound having antimicrobial activity, which may be an organic molecule, an inorganic or organic ionic material or a particulate material.

Step (b) can be performed by a variety of different means. The presence of water can be achieved using water-containing solvents for dissolving components (A) and / or (B), for example acetone, which are preferred as solvents. Thereby, the water required to perform the hydrolysis and initiate the polycondensation is essentially present in the system. Water may also be added separately before step (b).

Throughout the present invention the water content is determined by Karl Fischer Titration, preferably by Karl Fischer whole titration according to ISO 760: 1978.

The preferred water content in step (b) is determined by comparison with the weight of the alkoxysilane (B2). Suitable water contents in step (b) range from 5 to 100 parts by weight based on 100 parts by weight of alkoxysilane (B2). Preferably, the water in step (b) is present in an amount of from 8 to 50 parts by weight, particularly preferably from 10 to 35 parts by weight, very particularly preferably from 10 to 25 parts by weight, based on 100 parts of alkoxysilane (B2). .

Step (b) can be carried out at room temperature or at an increased temperature of 30 to 100 ° C., in particular 30 to 60 ° C. Step (b) can be carried out simultaneously at normal pressure or under a vacuum of 0.1 to 300 mbar, in particular 1 to 100 mbar. Step (b) can also be represented as a drying process in which hydrolysis and polycondensation occur essentially. Preference is given to performing step (b) so that a coating is formed. That is, the formation of the composition of the invention and the coating on the substrate takes place simultaneously.

The hydrolysis and polycondensation according to step (b) can optionally be catalyzed by a catalyst. Suitable catalysts such as acids and bases are known to those skilled in the art.

Step (b) results in a polymer network containing the antimicrobial actives (Z1). The antimicrobial active material (Z1) is not covalently bound to the silica network obtained during step (b) and in certain embodiments can be released automatically or upon triggering. Step (b) involves condensing the hydrolyzed siloxy group to form a silica network covalently bonded to the polyurethane containing the antimicrobial active material (Z1) in an intervening but not covalently bonded form. Preferably, the composition of the present invention retains the antimicrobial active material (Z1) and preferably releases it in the presence of water.

Antibacterial (Z)

The antimicrobial agent (Z) is a single antimicrobial active compound (Z1), a mixture of two or more different antimicrobial active compounds (Z1) or one or more antimicrobial active compounds in a carrier material (Z2) or on a carrier material (Z2), which are present in particulate form. It may consist of a mixture of (Z1).

According to the invention, it is essential that at least one antimicrobial active substance (Z1) is non-reactive during step (b). The term "non-reactive" means that the antimicrobial active material (Z1) is unable to react during step (b), ie not able to react with the prepolymer during the hydrolysis and polycondensation reactions in the presence of water. The terms “reactivity” and “reaction” refer to chemical reactions, ie, the formation of chemical bonds, as opposed to physical interactions such as capture. That is, "non-reactive during step (b)" means that no chemical bond to the antimicrobial active material (Z1) is formed substantially during step (b).

Step (b) preferably comprises further polymerization of the prepolymer by hydrolysis and polycondensation of component (B2) covalently bound to the prepolymer.

Preferably the antimicrobial active material (Z1) does not contain any functional groups capable of reacting with the Si-OH groups which are preferably present as intermediates in step (b). That is, the antimicrobial actives are not covalently bound to the inorganic portion of the hybrid network formed during step (b).

In principle, any antibacterial agent (Z) can be used under the conditions defined above.

In a preferred embodiment, the antimicrobial agent (Z) contains an antimicrobial active material (Z1) and also a particulate carrier material (Z2). In certain embodiments, the carrier material (Z2) may contain on the surface reactive groups that can react during step (b).

According to a first preferred embodiment (hereinafter referred to as "PE-1"), the antimicrobial agent (Z) comprises silver ions as the antimicrobial active material (Z1) and from the group of zeolites and polymer hydrogels as the particulate carrier material (Z2) Contains the selected one.

According to a second preferred embodiment (hereinafter referred to as "PE-2"), the antibacterial agent (Z) has a number average particle size of 1 to 1 selected from (i) zinc oxide and (ii) titanium dioxide containing AgBr and apatite. 500 nm particulate antimicrobial actives (Z1).

 Titanium dioxide encapsulated with AgBr and apatite is known to those skilled in the art. AgBr is known to increase the photocatalytic properties and / or antimicrobial efficacy of titanium dioxide. Apatite encapsulation is known to help prevent degradation in the vicinity of organic polymers.

According to a third preferred embodiment (hereinafter referred to as "PE-3"), the antibacterial agent (Z1) is selected from one or more of the group consisting of quaternary ammonium salts and 2-bromo-2-nitropropane-1,3-diol do.

In the following, preferred embodiments PE-1, PE-2 and PE-3 are discussed in detail.

According to a preferred embodiment PE-1, the antimicrobial agent (Z) comprises silver ions as the antimicrobial active material (Z1) and comprises a zeolite and a polymer hydrogel as the particulate carrier material (Z2).

In principle, any zeolite capable of retaining silver ions is suitable as the particulate carrier material (Z2) of the present invention. Zeolite particles that retain silver ions with antibacterial properties are known in the art. For example, silver zeolites that can be used for the purposes of the present invention are described in US-P 4911898, US-P 4911899, US-P 4938955, US-P 4906464, US-P 4775585 and WO 03/055314. It is described in the issue.

Polymeric hydrogels that retain silver ions are also known in the art. In principle, any polymer hydrogel capable of retaining silver ions can be used as the particulate carrier material (Z2) of the present invention.

The term “gel” refers to a substance in which the polymer molecules contained therein, ie, the solid and liquid phases of long chain molecules, are linked together to form a three-dimensional network. The polymer network is interposed in the liquid medium. The gel preferably has two continuous phases. Hydrogels refer to gels in which the liquid phase is water.

The polymer backbone of the hydrogel is typically formed by hydrophilic monomer units and may be neutral or ionic. Examples of neutral and hydrophilic monomer units include ethylene oxide, vinyl alcohol, (meth) acrylamide, N-alkylated (meth) acrylamide, N-methylol (meth) acrylamide, N-vinylamide, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-methylformamide, hydroxyalkyl (meth) acrylates such as hydroxyethyl methacrylate, vinylpyrrolidone; Polyethylene glycol monoallyl ethers, allyl ethers, (meth) acrylic acid esters of polyethylene glycol; Sugar units such as glucose or galactose. Examples of cationic hydrophilic monomer units are ethyleneimine (protonated form), diallyldimethylammonium chloride and trimethylammonium propylmethacrylamide chloride. Examples of the anionic monomer unit include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, 2-methacryloyloxyethane Sulfonic acid, 4-vinylbenzenesulfonic acid, allylsulfonic acid, vinyltoluenesulfonic acid and vinylbenzenephosphonic acid (all compounds mentioned are in aprotic form).

Hydrogels suitable as particulate carrier materials (Z2) can also be obtained by the polymerization of unsaturated acids such as acrylic acid, methacrylic acid and / or acrylamidopropane sulfonic acid in the presence of small amounts of various olefinically unsaturated compounds. . Suitable hydrogels are in particular specific organosilicon comonomers, for example tris (2-acetoxyethyldimethylsilyloxy) silylpropyl acrylate and / or methacrylate, tris (2-carboxyethyldimethylsilyloxy) silylpropyl acrylate And / or methacrylates, tris (3-hydroxypropyldimethylsilyloxy) silylpropyl acrylate and / or methacrylates, acrylates and methacrylates of fluorosubstituted functional alkyl / aryl siloxanes such as tris ( 3,3,3-trifluoropropyl dimethylsilyloxy) silyl propyl acrylate and / or methacrylate, tris [3-heptafluoroisopropoxy propyl)] dimethylsilyloxy silylpropyl acrylate and / or methacryl Latex, and tris (pentafluorophenyl dimethylsilyloxy) silyl propyl acrylate and / or methacrylate. Other hydrogels already known as superabsorbent polymers are also suitable. Such hydrogels are described, for example, in US-P 4,057,521, US-P 4,062,817, US-P 4,525,527, US-P 4,286,082, US-P 4,340,706 and US-P 4,295,987.

Hydrogels obtainable by graft copolymerization of olefinically unsaturated acids on different matrices, such as polysaccharides, polyalkylene oxides, and also derivatives thereof, are also suitable as particulate carrier materials (Z2). Such graft copolymers are known, for example, from US Pat. No. 5,011,892, US Pat. No. 4,076,663 and US Pat. No. 4,931,497.

Hydrogels are generally milled after drying using known contact or convective drying methods. Examples of contact dryers are hotplates, thin films, cans, contact belts, sheave drums, screws, tumbles or contact disk dryers. Examples of convection dryers include trays, chambers, channels, flat webs, plates, rotating drums, free-fall shafts, sheave belts, streams, atomization, fluidized beds, moving beds, paddles or spherical bed dryers (Kirk-Othmer 7 326-398; (3rd) 1, 598-624; 8, 75-130, 311-339; 5, 104-112; Ullmann 1, 529-609; 11, 642 ff .; (4th) 2, 698-721]; [vt Industrielle Praxis: "Fortschritte auf dem Gebiet der Einbandtrockner, Teil 1: Auslegungsverfahren, E. Tittmann; Research Disclosure 96-38363:" Drying of Pasty Materials using a Continuous Through-Circulation Belt Dryer "].

Hydrogels used in the present invention are preferably weakly crosslinked. As the crosslinking agent, vinyl, non-vinyl or dimodal crosslinking agents may be used alone, in a mixture, or in various combinations. Polyvinyl crosslinkers commonly known in the art for use in superabsorbent polymers are advantageously used. Preferred compounds having at least two polymerizable double bonds include di- or polyvinyl compounds such as divinyl benzene, divinyl toluene, divinyl xylene, divinyl ether, divinyl ketone and trivinyl benzene; Di- or polyesters of unsaturated mono- or polycarboxylic acids with polyols, such as polyols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, Di- or tri- (meth) acrylic acid esters of trimethylol propane, glycerin, polyoxyethylene glycol and polyoxypropylene glycol; Unsaturated polyesters obtainable by reacting any of the aforementioned polyols with an unsaturated acid such as maleic acid; Di- or polyesters of polyols derived from the reaction of unsaturated mono- or polycarboxylic acids with C ₂ -C ₁₀ polyhydric alcohols and 2 to 8 C ₂ -C ₄ alkylene oxide units per hydroxyl group, such as trimethyl All propane hexaethoxyl triacrylate; Di- or tri- (meth) acrylic acid esters obtainable by reacting polyepoxides with (meth) acrylic acid; Bis (meth) acrylamides such as N, N-methylene-bisacrylamide; Polyisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, 4,4'-diphenyl methane diisocyanate and NCO-containing preparatives obtained by reacting such diisocyanates with active hydrogen atom containing compounds having hydroxyl group containing monomers Carbamyl esters obtainable by reacting polymers such as di- (meth) acrylic acid carbamyl esters obtainable by reacting the above-mentioned diisocyanates with hydroxyethyl (meth) acrylates; Di- or poly (meth) allyl ethers of polyols such as alkylene glycols, glycerol, polyalkylene glycols, polyoxyalkylene polyols and carbohydrates such as polyethylene glycol diallyl ethers, allylated starches, and allylated celluloses; Di- or poly-allyl esters of polycarboxylic acids such as diallyl phthalate and diallyl adipate; And mono (meth) allyl esters of polyols and esters of unsaturated mono- or polycarboxylic acids, such as allyl methacrylate or (meth) acrylic acid esters of polyethylene glycol monoallyl ethers.

Preferred classes of crosslinking agents include, for example, bis (meth) acrylamides; Allyl (meth) acrylate; Di- or poly-esters of (meth) acrylic acid and polyols such as diethylene glycol diacrylate, trimethylol propane triacrylate, and polyethylene glycol diacrylate; And di- or polyesters of polyols derived from the reaction of unsaturated mono- or poly-carboxylic acids with C ₁ -C ₁₀ polyhydric alcohols and 2 to 8 C ₂ -C ₄ alkylene oxide units per hydroxyl group, Such as ethoxylated trimethylol propane triacrylate.

The antimicrobial agent (Z) according to the preferred embodiment PE-1 contains silver ions as the antimicrobial active substance (Z1). The antimicrobial active substance (Z1) is preferably present as a silver salt.

Examples of silver salts include, for example, silver acetate, silver acetylacetonate, silver azide, silver acetylide, silver arsenate, silver benzoate, silver bifluoride, silver monofluorolide, silver fluoride, silver bor Fluoride, silver bromate, silver bromide, silver carbonate, silver chloride, silver chlorate, silver chromate, silver citrate, silver cyanate, silver cyanide, silver- (cis, cis-1,5-cyclooctadiene) -1,1,1,5,5,5, -hexafluoroacetylacetonate, silver dichromate tetrakis- (pyridine) -complex, silver diethyldithiocarbamate, silver (I) fluoride, silver (II) fluoride, silver-7,7-dimethyl-1,1,1,2,2,3,3-heptafluoro-4,6-octadionate, silver hexafluoroantimonate, silver hexa Fluoroarsenate, silver hexafluorophosphate, silver iodate, silver iodide, silver isoty Cyanate, silver potassium cyanide, silver lactate, silver molybdate, silver nitrate, silver nitrite, silver (I) oxide, silver (II) oxide, silver oxalate, silver perchlorate, silver perfluorobutyrate, Silver perfluoropropionate, silver permanganate, silver perenate, silver phosphate, silver picrate monohydrate, silver propionate, silver selenate, silver selenide, silver selenite, silver sulfadiazine, silver Sulfate, silver sulfide, silver sulfite, silver telluride, silver tetrafluoroborate, silver tetraiodomercurate, silver tetratungstenate, silver thiocyanate, silver-p-toluenesulfonate, trifluoro Methanesulfonic acid silver salt, trifluoroacetic acid silver salt and silver vanadate. Mixtures of various silver salts may also be used. Preferred silver salts are silver acetate, silver benzoate, silver bromate, silver chlorate, silver lactate, silver molybdate, silver nitrate, silver nitrite, silver (I) oxide, silver perchlorate, silver permanganate, Silver selenate, silver selenite, silver sulfadiazine and silver sulfate. Most preferred silver salts are silver acetate and silver nitrate. Mixtures of silver salts may also be used.

Preferred silver content in the hydrogel is from 0.07 to 0.7% by weight, based on the total dry weight of the hydrogel.

According to a preferred embodiment PE-2, the antibacterial agent (Z) comprises a particulate antimicrobial active substance (Z1) having a number average particle size of 1 to 500 nm selected from zinc oxide and titanium dioxide containing AgBr and apatite.

The number average particle size represents the value measured by TEM measurement in combination with image analysis.

The number average particle size of the particulate antimicrobial active substance as component (Z1) is preferably in the range of 5 to 100 nm, in particular 10 to 50 nm, particularly preferably 15 to 45 nm and very particularly preferably 20 to 40 nm. .

Preference is given to using stabilized particles of antimicrobial actives (Z1). When Z 1 is zinc oxide, stabilization with an acrylic polymer is preferred.

Preference is also given to using zinc oxide doped with a dopant as described in US-A 2005/0048010.

Dopants can be added to the zinc oxide dispersion by means known to those skilled in the art. Suitable dopants for zinc oxide are, in particular, metal ions having one more electron or one less electron in the outer shell. Particularly suitable are main group metals and sub group metals in the oxidation state + III. Very particular preference is given to boron (III), aluminum (III), gallium (III) and indium (III). The metal can be added to the dispersion in the form of a soluble salt, and the choice of metal depends on whether or not it is dissolved in the dispersant at the desired concentration. For aqueous dispersions, many inorganic salts or complexes such as carbonates, halides, salts with EDTA, nitrates, salts with EDTA, acetyl acetonates and the like are suitable. Doping with precious metals such as palladium, platinum, gold and the like is also possible.

Particular preference is given to using surface-modified zinc oxide nanoparticles as antimicrobial actives (Z1). Surface modification of ZnO nanoparticles is known to those skilled in the art and is described, for example, in US-A 2006/0210495, which is incorporated herein by reference. Surface modification is preferably obtained by applying the surface modifier to ZnO nanoparticles, in particular to nanoparticle containing dispersions. In particular, suitable surface modifiers are disclosed in paragraphs 89 (p. 5) to 183 (p. 6) of US-A 2006/0210495.

It is also possible to modify the surface of the ZnO nanoparticles using polymers as described in US-A 2007/0243145, which is incorporated herein by reference.

The polymer used for the surface modification of ZnO nanoparticles for the purposes of the present invention is preferably selected from the copolymers described in paragraphs 18 (side 2) to 35 (side 3).

Suitable titanium dioxides containing AgBr and apatite are described in M. R. Elahifard, S. Rahimnejad, S. Haghighi, M. R. Gholami, J. Am. Chem. Soc 2007; 129 (31); 9552-9553.

Preferably, TiO ₂ used in the present invention is surface modified, in particular surface modified by silane as surface modifier.

Several suitable silanes as surface modifiers are described in the literature, especially those incorporated herein by reference in their entirety.

US-P 6,013,372, column 13 (row 54) to column 14 (row 54),

US Pat. No. 6,663,851, column 2 (row 9) to column 2 (row 54), and

US-A 2006/0159637, paragraph 44 (p. 2) to paragraph 83 (p. 3)

Listed in

Mixtures of two or more of the aforementioned silanes can be used for surface modification.

Preference is also given to using photocatalysts with the antibacterial enhancer described in US-P 6,013,372, especially page 15, the contents of which are incorporated herein by reference.

It is further preferred to use doped photocatalysts as described in US-P 6013372, page 15, lines 25-30.

U.S. Pat.Nos. 6,673,717, 7859,11, and 5,559,15 describe the doping of titanium dioxide with suitable nitrogen, fluorine and carbon, too.

In one preferred embodiment, TiO ₂ is coated with calcium apatite as described in US-A 2007/0154378 (particularly on pages 2 and 15 and 16, paragraphs 2), incorporated herein by reference.

According to a third preferred embodiment (“PE-3”), the antimicrobial agent (Z1) is selected from at least one of the group consisting of quaternary ammonium salts and 2-bromo-2-nitropropane-1,3-diol.

Preferred quaternary ammonium salts are benzyl-alkyldimethyl ammonium chloride, [2-[[2-[(2-carboxyethyl) (2-hydroxyethyl) amino] ethyl] amino] -2-oxo-ethyl] coco alkyldimethyl ammonium Hydroxide, benzyl-C _{12-14 -alkyldimethyl} ammonium chloride, benzyl-C _{12-16 -alkyldimethyl} ammonium chloride, benzyl-C _{12-18 -alkyldimethyl} ammonium chloride, C _12-14 -alkyl [(ethylphenyl ) Methyl] dimethyl ammonium chloride, reaction product of nC _{10 -16} -alkyltrimethylenediamine and chloroacetic acid, di-C _{8-10 -alkyldimethyl} ammonium chloride, dialkyl (C _8-18 ) dimethyl ammonium compound, diddecyldimethyl Ammonium chloride, cetylpyridinium chloride, biphenyl-2-ol, bronopol, cetylpyridinium chloride, chlorocresol, chloroxyleneol, D-gluconic acid and N, N "-bis (4-chlorophenyl) -3, Evolution of 12-Diimino-2,4,11,13-tetraazatetradecanediamidine (2: 1) Compound, ethanol, formaldehyde, formic acid, glutaraldehyde, hexa-2,4-dienoic acid, 1-phenoxypropan-2-ol and 2-phenoxypropanol, oligo- (2- (2-ethoxy) Methoxyethyl guanidinium chloride), pentapotassium bis (peroxymonosulfate) bis (sulfate), 2-phenoxyethanol, ortho-phthalaldehyde, 6- (phthalimido) peroxyhexanoic acid, poly ( Hexamethylenediamine guanidinium chloride), potassium (E, E) -hexa-2,4-dienoate, propan-1-ol, propan-2-ol, tetrakishydroxymethyl-phosphonium salt, ortho -Phenylphenol, and salts of ortho-phenylphenol, 1- (3-chloroallyl) -3,5,7-triaza-1-azoniaadamantane salt, (5-chloro-2,4-dichloro Phenoxy) -phenol, 3,4,4'-trichlorocarbanilide (triclocarban), o-benzo-p-chlorophenol, p-hydroxybenzoate, 2- (thiocyanomethylthio) benzothia Sol, 3,5-dimethyl-1,3,5-thiadiazin-2-thione, 2,4-dichlorobenzyl alcohol.

2-bromo-2-nitropropane-1,3-diol is particularly preferred as the antimicrobial active substance (Z1).

The following preferred embodiments refer to the preferred embodiments PE-1, PE-2 and PE-3 outlined above.

Preferably, the antimicrobial agent (Z) is present in an amount of 1 to 10% by weight, based on the total dry weight of the composition.

Total dry weight refers to the weight of the composition after solvent removal.

In one preferred embodiment, the composition according to the invention further contains an antimicrobial component (Z ′) which can react with component (A) and / or (B) in the presence of water in step (b). As a result, the antimicrobial component (Z ') is covalently bound to the inorganic part of the resulting hybrid network.

Preferred antibacterial agents (Z ′) comprise alkoxysilane moieties and are represented by the following formula (II).

<Formula II>

In the above formula,

R ₁ is a C ₁ -C alkyl group, preferably a C ₈ -C ₃₀ alkyl group,

R ₂ and R ₃ , R ₄ and R ₅ are each independently a C ₁ -C ₃₀ alkyl group or hydrogen,

- X is a counter ion, such as Cl ^-, Br ^-, I ^- is ^- or CH ₃ COO.

Examples of organosilicon quaternary ammonium salt compounds for use according to the invention include 3- (triethoxysilyl) -propyl-dimethyloctadecylammonium chloride, 3- (trimethoxysilyl) propyl-methyl-dioctyl ammonium chloride , 3- (trimethoxysilyl) propyl-dimethylceyl ammonium chloride, 3- (trimethoxysilyl) -propyl-methyldidecyl ammonium chloride, 3- (trimethoxysilyl) propyldimethyldodecyl ammonium chloride, 3- (Trimethoxysilyl) -propyl-methyldidodecyl ammonium chloride, 3- (trimethoxysilyl) propyl-dimethyltetradecyl ammonium chloride, 3- (trimethoxysilyl) propyl-methyldihexadecyl ammonium chloride and 3- (Trimethoxysilyl) propyl-dimethyloctadecyl ammonium chloride.

The antimicrobial agent (Z ′) is advantageously present in an amount from about 0.1% to about 50% by dry weight of the composition. The preferred amount of agent is 1% to 10% of the composition based on the dry weight of the composition.

catalyst

The reaction between polyisocyanate A and binder compound B is preferably carried out by using a catalyst.

Non-limiting examples of suitable catalysts include tertiary amines such as N, N-dimethylaminoethanol, N, N-dimethyl-cyclohexamine-bis (2-dimethylaminoethyl) ether, N-ethylmorpholine, N, N, N ', N', N "-pentamethyl) -diethylenetriamine and 1-2 (hydroxypropyl) imidazole, and metallic catalysts such as tin, stannous octoate, dibutyl tin dilaurate , Dioctyl or dibutyl tin dilaurate, dibutyl tin mercaptide, ferric acetylacetonate, lead octoate and dibutyl tin diricinoleate, preferably the catalyst is tin-based. Is dioctyl or dibutyl tin dilaurate.

Additional ingredients

Preferably, the composition according to the invention further comprises a solvent (D).

Examples of solvents (D) are alcohols, esters, ester alcohols, ethers, ether alcohols, aromatic and / or (cyclo) aliphatic hydrocarbons and mixtures thereof, and halogenated hydrocarbons. It is also possible to introduce the alcohol into the mixture via the amino resin.

Preferred are alkanoic acid alkyl esters, alkanoic acid alkyl ester alcohols, alkoxylated alkanoic acid alkyl esters and mixtures thereof.

Examples of esters include n-butyl acetate, ethyl acetate, 1-methoxyprop-2-yl acetate and 2-methoxyethyl acetate, and also ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol Or monoacetyl and diacetyl esters of tripropylene glycol such as butyl glycol acetate. Further examples are also carbonates, such as preferably 1,2-ethylene carbonate, 1,2-propylene carbonate or 1,3-propylene carbonate.

Ethers are, for example, tetrahydrofuran (THF), dioxane, and dimethyl, diethyl or di-n-butyl ether of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol to be.

Alcohols are, for example, methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dode Canol (lauryl alcohol), 2-ethylhexanol, cyclopentanol or cyclohexanol.

Alkanoic ester alcohols are, for example, poly (C ₂ to C ₃ ) alkylene glycol (C ₁ to C ₄ ) monoalkyl ether acetates. Ether alcohols are, for example, poly (C ₂ to C ₃ ) alkylene glycol di (C ₁ to C ₄ ) alkyl ethers, dipropylene glycol dimethyl ether, preferably butyl glycol.

Aromatic hydrocarbon mixtures include predominantly aromatic C ₇ to C ₁₄ hydrocarbons and may include boiling points in the range from 110 to 300 ° C., toluene, o-, m- or p-xylene, trimethylbenzene isomers, tetramethylbenzene isomers Especially preferred are ethylbenzene, cumene, tetrahydronaphthalene, and mixtures comprising them.

Examples thereof include Solvesso® grades from ExxonMobil Chemical, in particular Solvesso® 100 (CAS No. 64742-95-6, predominantly C ₉ and C ₁₀ aromatics, in the range of about 154 to 178 ° C). Boiling point), 150 (boiling point ranging from about 182 to 207 ° C.) and 200 (CAS No. 64742-94-5), and also Shellsol® grade from Shell, Petrochem Carless Caromax® grade, for example Carromax® 18, or a product from DHC, for example Hydrosol® A / 170. Hydrocarbon mixtures comprising paraffins, cycloparaffins and aromatics may also contain Kristalloel (e.g., Crystalloel 30, boiling point or Crystalloel 60: CAS No. 64742-82-1), white oil, in the range of about 158-198 ° C. (white spirit) (same CAS number 64742-82-1) or solvent naphtha (hard: boiling point in the range of about 155 to 180 ° C., heavy: boiling point in the range of about 225 to 300 ° C.). . The aromatic content of such hydrocarbon mixtures is generally above 90% by weight, preferably above 95% by weight, more preferably above 98% by weight, very preferably above 99% by weight. In particular it may be advisable to use hydrocarbon mixtures having a reduced naphthalene content.

The density of the hydrocarbon at 20 ° C. according to DIN 51757 may be less than 1 g / cm ³ , preferably less than 0.95 g / cm ³ , more preferably less than 0.9 g / cm ³ .

The aliphatic hydrocarbon content is generally less than 5% by weight, preferably less than 2.5% by weight, more preferably less than 1% by weight.

Halogenated hydrocarbons are, for example, chlorobenzene and dichlorobenzene, or isomer mixtures thereof.

(Cyclo) aliphatic hydrocarbons are, for example, decalin, alkylated decalin, and isomeric mixtures of linear or branched alkanes and / or cycloalkanes.

Preference is given to n-butyl acetate, ethyl acetate, 1-methoxyprop-2-yl acetate, 2-methoxyethyl acetate, and mixtures thereof.

Mixtures of this type can be prepared in a volume ratio of 10: 1 to 1:10, preferably in a volume ratio of 5: 1 to 1: 5, more preferably in a volume ratio of 1: 1.

Preferred examples are butyl acetate / xylene, 1: 1 methoxypropyl acetate / xylene, 1: 1 butyl acetate / solvent naphtha 100, 1: 2 butyl acetate / Solveso® 100, and 3: 1 crystalloel 30 / shellsol ® A.

Alcohols are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, pentanol isomer mixtures, hexanol isomer mixtures, 2-ethylhexanol or octanol.

Examples of additional conventional coating additives (E) that can be used include antioxidants, stabilizers, activators (promoters), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surfactants, viscosity modifiers, plasticizers or Chelating agents are included.

Suitable thickeners other than free-radically (co) polymerized (co) polymers include conventional organic and inorganic thickeners such as hydroxymethylcellulose or bentonite.

Examples of chelating agents that can be used include ethylenediamineacetic acid and its salts, and β-diketones.

Suitable fillers include silicates, for example silicates obtainable by silicon tetrachloride hydrolysis, such as Aerosil® from Degussa, silicate, talc, aluminum silicate, magnesium silicate, calcium carbonate and the like. do.

Suitable stabilizers are conventional UV absorbers such as oxanilides, triazines and benzotriazoles (the latter available in the Tinuvin® grade from Ciba-Spezialitaetenchemie) and benzophenones It includes. It can be used alone or in a suitable free-radical scavenger, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof ( For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate). Stabilizers are typically used in amounts of 0.1% to 5.0% by weight based on the solid components included in the formulation.

Pigments may likewise be included. With reference to DIN 55943, pigments according to CD Roempp Chemie Lexikon-Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995 are particulate organic or inorganic, dyeable or non-staining colorants which are virtually insoluble in the application medium.

Virtually insoluble herein means a solubility of less than 1 g, preferably less than 0.5 g, more preferably less than 0.25 g, very preferably less than 0.1 g, in particular less than 0.05 g per 1000 g of application medium at 25 ° C. it means.

Examples of pigments include any desired system of absorbing pigments and / or effect pigments, preferably absorbing pigments. There is no limitation with regard to the number and selection of pigment components. They can be adapted as required for specific requirements, for example the desired color impression.

By effect pigment is meant all pigments having a platelet-shaped structure and imparting a particular decorative color effect to the surface coating. Effect pigments include, for example, all effect-imparting pigments that can normally be used in vehicle finishing and industrial coatings. Examples of effect pigments of this type include pure metal pigments such as aluminum, iron or copper pigments; Interference pigments such as titanium dioxide-coated mica, iron oxide-coated mica, mixed oxide-coated mica (eg coated with titanium dioxide and Fe ₂ O ₃ , or coated with titanium dioxide and Cr ₂ O ₃ ), Metal oxide-coated aluminum, or liquid crystalline pigment.

Color-granting pigments are conventional organic or inorganic absorbing pigments that can be used, for example, in the coatings industry. Examples of organic absorbing pigments are azo pigments, phthalocyanine pigments, quinacridone pigments and pyrrolopyrrole pigments. Examples of inorganic absorbing pigments are iron oxide pigments, titanium dioxide and carbon black.

The solids content of the coating composition of the present invention is defined for the purposes of the present specification as the ratio of the total amount of components (A) and (B) to the total amount of components (A), (B) and (D). The solids content according to the invention is for example 25% to 90% by weight, preferably 40% to 80% by weight.

Components (A) and (B) are usually in a ratio of 0.2: 1 to 5: 1 (based on the ratio of NCO groups in (A) to OH groups in (B)), preferably 0.4: 1 to 3 It is used in a ratio of 1: 1, more preferably in a ratio of 0.5: 1 to 2: 1, very preferably in a ratio of 0.8: 1 to 1.2: 1.

apply

The compositions of the present invention can advantageously be used to prepare antimicrobial coatings. The compositions of the invention are useful as coatings and can be used in particular as clearcoats and / or basecoats in primer, topcoat or clearcoat / basecoat compositions. It is also useful in spray applications.

The composition results in a fast, durable coating with extended pot life and excellent curing power. The curable composition of the present invention provides a clearcoat having improved scratch resistance. The compositions of the invention can also be used in principle as adhesives, elastomers and plastics.

The coating materials of the present invention are used to coat substrates including wood, paper, textiles, leather, nonwovens, plastic surfaces, glass, ceramics, mineral building materials such as cement moldings and fiber-cement slabs, coated or uncoated metals. Suitable. Particular preference is given to the use of curable compositions for coating plastics or metals in the form of sheets, more preferably for the coating of surfaces made of metals.

Antimicrobial compositions, and coatings comprising such antimicrobial compositions, are particularly suitable for the hospital environment, medical equipment, water treatment plants, food service and packaging sectors, pharmaceutical laboratories, child care facilities, and other fields requiring additional protection against microorganisms. The antimicrobial composition, and the coating comprising the antimicrobial composition, are advantageously used in food equipment, for example mixing balls, serving trays, salad bars, sinks, walk-in, freezers, display cases and serving counters, household equipment. For example refrigerators, washers, dryers, food disposal and waste compactors, food processing equipment, for example grinders, trays, conveyors, storage boxes, slicers and food processing equipment, medical equipment, for example Instrument trays, racks, sterilization equipment, bedpans, counter topes, examination tables, carts, bed and lighting fixtures, hospitals as well as public and private interior equipment, e.g. pushplates , In kickplates, towel dispensers, doors, escalators, elevators, and toilet equipment, parts of vehicles, for example vehicle interior parts and surfaces, It can be used as an interior part of the air and the surface, and the train interior parts and surfaces.

The substrate is coated with the coating material of the present invention according to conventional techniques known to those skilled in the art, which apply one or more coating materials or coating formulations of the present invention to the target substrate in the desired thickness and, if appropriate, heated (dry) Removing volatile components of the coating material. This process can be repeated one or more times as necessary. It can be applied to the substrate in a known manner, for example by spraying, troweling, knife coating, brushing, rolling, roller-coating or pouring. The coating thickness is generally in the range of about 3 to 1000 g / m ² , preferably 10 to 200 g / m ² . Curing can then be carried out.

Curing generally follows application of the coating material to the substrate, where appropriate at temperatures below 80 ° C., preferably from room temperature to 60 ° C., more preferably from room temperature to 40 ° C., up to 72 hours, preferably 48 hours. Or less preferably 24 hours, very preferably 12 hours or less, in particular 6 hours or less, and the applied coating is dried under an oxygen-containing atmosphere, preferably air or an inert gas, from 80 to It is achieved by heat treatment (curing) at a temperature of 270 ° C, preferably 100 to 240 ° C, more preferably 120 to 180 ° C. Curing of the coating material depends on the amount of coating material applied and through high energy radiation, heat transfer from the heated surface, or through convection of the gaseous medium, for example over a few seconds, for example with NIR drying. In the case of coil coatings combined, for example over 5 hours or less, for high-build systems on temperature sensitive materials, usually at least 10 minutes, preferably at least 15 minutes, more preferably at least 30 minutes Very preferably according to the crosslinking energy introduced over a period of at least 45 minutes. Drying involves the removal of the solvent present essentially, and additionally there may even be a reaction with the binder in this step, while curing essentially comprises a reaction with the binder.

In addition to or in place of thermal curing, curing can also be carried out using IR and NIR radiation, wherein the NIR radiation can produce electromagnetic radiation having a wavelength in the range of 760 nm to 2.5 μm, preferably 900 to 1500 nm. Indicates.

Curing is carried out for a period of 1 second to 60 minutes, preferably 1 minute to 45 minutes.

Examples of substrates suitable for the coating materials of the invention include thermoplastic polymers, in particular polymethyl methacrylate, polybutyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyvinylidene fluoride, polyvinyl chloride, polyester , Polyolefins, acrylonitrile-ethylenepropylene-diene-styrene copolymers (A-EPDM), polyetherimides, polyether ketones, polyphenylene sulfides, polyphenylene ethers or mixtures thereof.

In addition, polyethylene, polypropylene, polystyrene, polybutadiene, polyester, polyamide, polyether, polycarbonate, polyvinyl acetal, polyacrylonitrile, polyacetal, polyvinyl alcohol, polyvinyl acetate, phenolic resin, urea resin Mention may be made of melamine resins, alkyd resins, epoxy resins or polyurethanes, block or graft copolymers thereof, and blends thereof.

Preferably ABS, AES, AMMA, ASA, EP, EPS, EVA, EVAL, HDPE, LDPE, MABS, MBS, MF, PA, PA6, PA66, PAN, PB, PBT, PBTP, PC, PE, PEC, PEEK , PEI, PEK, PEP, PES, PET, PETP, PF, PI, PIB, PMMA, POM, PP, PPS, PS, PSU, PUR, PVAC, PVAL, PVC, PVDC, PVP, SAN, SB, SMS, UF , UP plastics (abbreviated according to DIN 7728) and aliphatic polyketones.

Particularly preferred substrates may be isotactic, syndiotactic or atactic, optionally polyolefins such as PP (polypropylene), SAN, which may optionally be unoriented or uniaxial or biaxially oriented (Styrene-acrylonitrile-copolymer), PC (polycarbonate), PVC (polyvinyl chloride), PMMA (polymethyl methacrylate), PBT (poly (butylene terephthalate)), PA (polyamide), ASA (acrylonitrile-styrene-acrylate copolymer) and ABS (acrylonitrile-butadiene-styrene-copolymer), and also their physical mixtures (blends). Particular preference is given to PP, SAN, ABS, ASA, and blends of ABS or ASA with PA or PBT or PC. Particular preference is given to polyolefins, PMMA and PVC.

Particular preference is given to ASA according to DE 196 51 350, and to ASA / PC blends. Likewise polymethyl methacrylate (PMMA) or impact-modified PMMA is preferred.

Further preferred substrates for coating using the coating materials of the present invention are metals. The metal is in particular already coated with another coating film, for example with an electrocoat, surfacer, primer or basecoat. Such coating films may be solvent-based, water-based or powder coating-based, crosslinked, partially crosslinked or thermoplastic, cured over their volume or wet-on-wet applied.

With regard to the type of metal, suitable metals can in principle be any desired metals. However, particularly suitable metals are metals or alloys which are commonly used as metallic materials for construction and which require protection against corrosion.

The surface is especially the surface of iron, steel, Zn, Zn alloys, Al or Al alloys. It may be the surface of a structure consisting only of the metal or alloy of interest. Alternatively, the structure may only be coated with this metal, and may itself consist of other types of materials, for example other metals, alloys, polymers or composite materials. It may be the surface of a casting made from galvanized iron or steel. In one preferred embodiment of the invention, the surface is a steel surface.

Zn alloys or Al alloys are known to those skilled in the art. One skilled in the art selects the nature and amount of alloy constituents depending on the desired end use application. Typical components of zinc alloys include in particular Al, Pb, Si, Mg, Sn, Cu or Cd. Typical components of aluminum alloys include in particular Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti. The alloy may also be an Al / Zn alloy in which Al and Zn are present in approximately equal amounts. Steel coated with this type of alloy is commercially available. The steel may comprise conventional alloying components known to those skilled in the art.

It is also contemplated to use the coating compositions of the invention for tin-plated iron / steel (tin) treatment.

The coatings obtainable from the curable compositions according to the invention exhibit excellent antibacterial properties.

It will be appreciated by those skilled in the art that under suitable conditions, in the presence of particularly suitable catalysts and water, the polyurethane-based polymers obtained according to the invention are polyurethane-polyurea-silica polymers.

Another subject of the invention is as a separate part

a) at least one polyisocyanate (A) as defined above,

b) at least one binder component (B) having two or more functional groups reactive to isocyanates, as defined above,

c) at least one isocyanate reactive alkoxysilane (C) as defined above and

d) at least one antimicrobial agent (Z) as defined above

It is a kit containing the curable composition containing.

<Examples>

The following abbreviations were used in the following examples:

AMSI: 3- [bis (2-hydroxyethyl) amino] propyl triethoxysilane

HDI: hexamethylene diisocyanate

BNP: 2-bromo-2-nitro-1,3-propanediol (bronopol)

PPG: Polypropylene Glycol

PD: 1,5-pentanediol

NIPAM: N-isopropylacrylamide

TEMED: N, N, N ', N'-tetramethylenediamine

MBA: N ', N-methylenebisacrylamide

AP: ammonium persulfate.

Polyurethane prepolymer ( HPP Preparation of A50):

1 g of hexamethylene diisocyanate (HDI) and 0.17 g of dibutyltin dilaurate were dried in a Schlenk flask under vacuum at 50 ° C. for 2 hours. In another flask, poly (propyleneglycol) (PPG) (2.7 g) and 0.84 g of 3- [bis (2-hydroxyethyl) amino] propyl triethoxysilane] (AMSI) were added and 50 ° C. in vacuo. Dried over. After 2 hours, 15 ml of acetone was added to the flask containing PPG and AMSI. The contents were transferred to another flask and then stirred at 50 ° C. for an additional 2 hours.

TiO ₂ Of AgBr Manufacture of Apatite:

1 g of TiO ₂ [Degussa P-25] and 0.05 g of hydroxyapatite were added to 100 ml of distilled water and the suspension was stirred. 1.2 g cetyl methyl ammonium bromide (CTAB) was then added to the suspension and stirring continued. Thereafter, 0.21 g of AgNO ₃ in 2.3 ml of NH ₄ OH (25 wt.% NH ₃ ) was added quickly thereto. The resulting suspension was stirred overnight at room temperature. The product was then filtered, washed with distilled water and dried at 80-110 ° C. Finally, the prepared photocatalyst was calcined at 500 ° C. for 3 hours in air.

Hydrogel  Produce:

NIPAM (0.80 g) and MBA (20 mg) were dissolved in 8.0 ml of H ₂ O under sonication. Then 1 ml of APS solution (10 mg / 1 ml H ₂ O) and 1 ml of TEMED solution (0.128 ml / 1 ml H ₂ O) were added to the prepared solution with stirring. A transparent hydrogel was obtained in a few minutes. The hydrogel was cut into small pieces and washed three times with H ₂ O. The hydrogel was then immersed in AgNO ₃ solution (100 mg / 20 ml H ₂ O) for 8 hours. After washing three times with H ₂ O, the Ag ⁺ -supported hydrogel was dried under vacuum at 45 ° C. for 24 hours.

Synthesis of Antimicrobial Coatings:

Example 1: Antimicrobial agent with 0.05 g of AJ-100, Agion® (Ag ⁺ -containing zeolite) distributed in 5 g of acetone solution of polyurethane prepolymer HPP-A50 obtained according to the above method, and An additional 50 ml of acetone was added and stirred for 1 hour. The water content of the mixture was 13 parts by weight relative to 100 parts by weight of AMSI. The resulting solution was then transferred to a polycarbonate slide in the form of a coating and dried in an oven at 100 ° C. for 2 hours.

Example 2: Same as Example 1 except 0.25 g of AJ-100 was used.

Example 3: Same as Example 1 except that 0.05 g of zinc oxide nanoparticles were used instead of AJ-100.

Example 4: Same as Example 3 except that 0.5 g of zinc oxide nanoparticles were used instead of AJ-100.

Example 5: Same as Example 1 except that 0.05 g of antimicrobial polymer hydrogel with silver ions was used instead of AJ-100.

Example 6: Same as Example 5 except for using 0.5 g of antimicrobial polymer hydrogel with silver ions instead of AJ-100

Example 7: Same as Example 1 except that 0.05 g of the antimicrobial agent TiO ₂ / AgBr / Apatite was used instead of AJ-100.

Example 8: Same as Example 7 except that 0.5 g of the antimicrobial agent TiO ₂ / AgBr / Apatite was used instead of AJ-100.

Example 9: Same as Example 1 except that 0.05 g of Bronopol (BNP) was used instead of AJ-100.

Example 10: Same as Example 10 except that 0.5 g of BNP was used instead of AJ-100.

Determination of Antimicrobial Activity

Tests for antimicrobial activity were performed according to Japanese standard JIS Z 2801: 2000-Test for antimicrobial activity and efficacy. Table 1 contrasts the antimicrobial activity of polyurethanes with different amounts of antimicrobial agents. The antimicrobial activity shown in Table 1 is based on the average number of viable cells immediately after inoculation on the coating without the antimicrobial agent, the average number of viable cells after 24 hours on the coating without the antimicrobial agent, and the antimicrobial agent, as indicated in the equation according to JIS Z 2801: 2000. Calculations were based on the average number of viable cells after 24 hours on the coating surface with the coating.

Claims (16)

(a)-(A) an isocyanate component containing two or more isocyanate groups on average per molecule
(B) a binder component having, on average, at least two functional groups reactive to isocyanates and comprising at least one alkoxysilane (B2)
To react to obtain a prepolymer, and then
(b)-water and
At least one antimicrobial agent (Z) comprising at least one antimicrobial active material (Z1) and optionally a particulate carrier material (Z2)
Hydrolyzing and polycondensing said prepolymer in the presence of at least one antimicrobial active material (Z1), wherein said step is non-reactive during step (b). The process of claim 1 wherein the water in step (b) is present in an amount of from 10 to 50 parts by weight relative to 100 parts by weight of the total dry weight of the prepolymer. The method according to claim 1 or 2, wherein the antimicrobial agent (Z) comprises silver ions as the antimicrobial active material (Z1) and selected from the group of zeolites and polymer hydrogels as the particulate carrier material (Z2). . The antimicrobial agent (Z) according to claim 1 or 2, wherein the antimicrobial agent (Z) is one selected from particles having a number average particle size of 1 to 500 nm and containing particles of (i) zinc oxide and (ii) titanium dioxide, AgBr and phosphite. Method containing the above fine particle antimicrobial active material (Z1). The antimicrobial agent (Z) according to claim 1 or 2, wherein the antimicrobial agent (Z) comprises an antimicrobial active substance (Z1) selected from one or more of the group consisting of quaternary ammonium salts and 2-bromo-2-nitropropane-1,3-diol. How to do. The isocyanate component (A) according to any one of claims 1 to 5, wherein the isocyanate component (A) is 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) -cyclohexane, 1, 6-diisocyanatohexane, 4,4'-di (isocyanatocyclohexyl) methane, and 3 (or 4), 8 (or 9) -bis (isocyanatomethyl) tricyclodecane and its And at least one of the isomeric mixtures. The method according to any one of claims 1 to 6, wherein the isocyanate component (A) comprises 1,6-diisocyanatohexane. 8. The process according to claim 1, wherein the binder component (B) comprises at least one binder (B1) selected from the group consisting of polyols and polyamines. 9. The method according to any one of claims 1 to 8, wherein the binder component (B) comprises at least one binder (B1) selected from the group consisting of polypropylene glycol and 1,5-pentanediol. 10. The alkoxysilane (B2) according to any one of claims 1 to 9, wherein the alkoxysilane (B2) comprises at least one according to formula (I), provided that the alkoxysilane (B2) contains at least two functional groups reactive to isocyanates. How to do.
<Formula I>

Where
n is an integer from 1 to 6,
R ¹ is H or C ₁ -C ₆ alkyl,
R ² and R ³ are independently —OH, OR ¹ or C ₁ -C ₆ alkyl,
R ⁴ and R ⁵ are independently H, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl or C ₁ -C ₆ aminoalkyl. The alkoxysilane (B2) according to any one of claims 1 to 10, wherein N- (3- (trimethoxysilyl) propyl) ethylenediamine, 1- (3- (trimethoxysilyl) propyl) di Ethylenetriamine, bis (3- (methylamino) propyl) trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Methyldimethoxysilane, γ-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, N-phenyl aminomethyl triethoxy silane and bis- (γ- Trimethoxysilylpropyl) amine and combinations thereof. The method according to claim 1, wherein the antimicrobial agent (Z) is present in an amount of 1 to 10% by weight, based on the total dry weight of the resulting composition. A composition obtainable according to any of the preceding claims. A coating comprising the composition of claim 13. As defined in any one of claims 1 to 12, respectively.
a) an isocyanate component (A) containing on average two or more isocyanate groups per molecule,
b) a binder component (B) containing on average two or more functional groups reactive to isocyanates,
c) at least one alkoxysilane reactive with isocyanates, and
d) at least one antimicrobial agent (Z)
A kit comprising a curable composition that contains as a separate portion for connecting applications. Use of the composition according to claim 13 for producing an antimicrobial coating.