WO2013110530A1

WO2013110530A1 - Radiation-curable anti-microbial coatings

Info

Publication number: WO2013110530A1
Application number: PCT/EP2013/050699
Authority: WO
Inventors: Reinhold Schwalm; Rupert Konradi; Christina Haaf; Herbert Platsch; Catharina Hippius
Original assignee: Basf Se; Basf Schweiz Ag
Priority date: 2012-01-27
Filing date: 2013-01-16
Publication date: 2013-08-01

Abstract

The present invention relates to a radiation-curable anti-microbial coatings, to a method for producing the same and to the use thereof.

Description

Radiation-curable antimicrobial coatings

The present invention relates to radiation-curable antimicrobial coatings, to a process for their preparation and to their use.

WO 2008/131715 discloses silane-functional reaction products of diols with isocyanato-propyltriethoxysilane, which lead to easily cleanable coatings in coating compositions.

WO 2008/132045 describes compounds which carry at least one quaternary ammonium group and at least one (meth) acrylate group. Such compounds are used in radiation-curable coating compositions and lead to biocidal coatings.

WO 2008/31596 describes coating compositions for the production of radiation-curable medical coatings in which hydrophilic multifunctional (meth) acrylamides are used. In order to achieve antimicrobial properties, antimicrobial compounds must be added to these coating compositions.

From DE 19921904 compounds for antimicrobial coating compositions are known which have silyl groups and (meth) acrylate groups.

From DE 19700081 radiation-curable, antimicrobial coating compositions are known from silylated (meth) acrylates, cinnamoylethyl (meth) acrylate, other radiation-curable monomers, such as (meth) acrylates and ammonium compounds. The disadvantage is that the effect of the antimicrobial coating compositions is relatively weak and predominantly based solely on an anti-adhesive instead of a biocidal effect. The object of the present invention was to provide radiation-curable coatings which can be designed with a fast and as complete as possible antimicrobial action and at the same time give coatings with good coating properties.

The object has been achieved by antimicrobial radiation-curable coatings, obtained by reaction of

- (A) at least one urethane (meth) acrylate, the

at least one (meth) acrylate group and

at least one quaternary ammonium group substituted by four radicals having in total at least 12 carbon atoms,

contains

(B) at least one hydrophilic reactive diluent,

(C) optionally at least one reactive diluent other than (B),

- - (D) optionally at least one photoinitiator and

- - (E) optionally at least one further paint additive. The radiation-curable antimicrobial coatings according to the invention exhibit a strong and rapid antimicrobial action which persists over a relatively long period of time, with simultaneously good coating properties, in particular hardness, of the coatings obtained therefrom.

The at least one urethane (meth) acrylate (A) are those

Urethane (meth) acrylates which

at least one (meth) acrylate group and

at least one quaternary ammonium group substituted by four radicals having a total of at least 12 carbon atoms,

contain.

The urethane (meth) acrylates (A) preferably have one to six, particularly preferably one to four, very particularly preferably one to three, in particular one to two and especially precisely one (meth) acrylate group.

In the context of this document, a (meth) acrylate group is understood as meaning a methacrylate or acrylate group, preferably an acrylate group. The urethane (meth) acrylates (A) preferably have one to four, particularly preferably one to three, very particularly preferably one to two and in particular exactly one quaternary ammonium group.

"Quaternary ammonium groups" within the meaning of the present specification are those which are substituted by three hydrocarbon radicals and are bonded to the urethane (meth) acrylate by a spacer. The number of carbon atoms in these quaternary ammonium groups is determined from the sum of the carbon atoms in the three hydrocarbon radicals and the carbon atoms in the spacer, taking into account only the carbon atoms between the nitrogen atom of the quaternary ammonium group and the first heteroatom.

The spacer comprises at least one carbon atom, preferably at least two carbon atoms.

In general, the spacer is not longer than ten carbon atoms, preferably not longer than six carbon atoms, and most preferably not longer than four carbon atoms.

If, for example, the quaternary ammonium group comprises a ring, the carbon atoms of the ring are of course only simply calculated. By this definition, a 2- (N, N, N-triethylammonium) ethyl group has eight carbon atoms and a 3- (N-ethyl piperidinium) propyl group has ten carbon atoms. In a preferred embodiment, the quaternary ammonium group has the following formula (I)

R ¹ R ² R ³ N ⁺ - R ⁴ - wherein

R ¹ , R ² and R ^{3 are} each independently of one another 1 to 20, preferably one to 15 carbon atoms having alkyl groups, 6 to 14, preferably 6 to 10, particularly preferably 6 carbon atoms having aryl groups or 7 to 20, preferably 7 to 15, particularly preferably 7 to 10 carbon atoms having aralkyl groups, wherein two of the radicals R ¹ to R ^{3 may} also be together part of a ring, and

R ^{4 is} a 1 to 10, preferably 2 to 6, particularly preferably 2 to 4 carbon atoms containing divalent hydrocarbon radical

mean.

Examples of alkyl groups having 1 to 20 carbon atoms are methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, 2-ethylhexyl , n-octyl, n-decyl, 2-propylheptyl, n-dodecyl, iso-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.

Examples of aryl groups having 6 to 14 carbon atoms are phenyl, α-naphthyl and β-naphthyl. Examples of aralkyl groups having from 7 to 20 carbon atoms are benzyl, phenethyl, 3-phenylpropyl, 4-phenylbutyl and 6-phenylhexyl.

Examples of divalent hydrocarbon radicals having 1 to 10 carbon atoms are 1, 2-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 2-butylene, 1, 3-butylene, 1, 4-butylene, 1, 6 Hexylene, 2-methyl-1,3-propylene, 2-ethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, 1,8-octylene and 1, 10-decylene.

The radicals R ¹ to R ³ are each, independently of one another, in each case alkyl groups.

In a preferred embodiment of the present invention, the groups R ¹ to R ⁴ in the quaternary ammonium groups of the formula (I) in total have at least 12 carbon atoms, preferably at least 14, more preferably at least 16 and most preferably at least 18 carbon atoms.

In a further preferred embodiment, at least one, preferably exactly one of the radicals R ¹ to R ^{3 has} at least 10 and preferably at least 12 carbon atoms. In a further preferred embodiment, one of the radicals R ¹ to R ^{3 has} at least 10 and preferably at least 12 carbon atoms and the other two in each case not more than 4, preferably not more than 2, carbon atoms. The compounds (A) are preferably urethane (meth) acrylates synthesized from (a1) at least one diisocyanate or polyisocyanate,

(a2) at least one compound having at least one, preferably exactly one opposite

Isocyanate group-reactive group and at least one (meth) acrylate group,

(a3) optionally at least one low molecular weight compound having at least two isocyanate-reactive groups,

(a4) optionally at least one high molecular weight compound having at least two opposite

Isocyanate-reactive groups,

(a5) at least one compound having at least one, preferably exactly one isocyanate-reactive group and at least one quaternary ammonium group and

(a6) optionally at least one compound having exactly one isocyanate-reactive group.

Isocyanate-reactive groups are preferably hydroxy, mercapto, or a primary or secondary amino groups, more preferably hydroxy or primary amino groups and most preferably hydroxy groups.

The compounds (A) preferably have a density of (meth) acrylate groups of at least 0.5 mol per 1000 g, particularly preferably from 1 to 5 and very particularly preferably from 2 to 4 mol per 1000 g.

The compounds (A) preferably have a density of ammonium groups of at least 0.07 mol per 1000 g, more preferably from 0.14 to 1 and most preferably from 0.14 to 0.5 mol per 1000 g.

The urethane (meth) acrylates (A) preferably have a number average molecular weight M _n of less than 5000, in particular less than 2000 and particularly preferably less than 1000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard). Components (a1)

Particularly suitable polyisocyanates as components (a1) for the polyurethanes of the invention are (cyclo) aliphatic diisocyanates and polyisocyanates based on (cyclo) aliphatic diisocyanates.

The term (cyclo) aliphatic in this document is short for cycloaliphatic or aliphatic. Cycloaliphatic isocyanates are those which contain at least one cycloaliphatic ring system.

Aliphatic isocyanates are those which contain exclusively straight or branched chains, ie acyclic compounds.

The polyisocyanates which can be used according to the invention have no aromatic groups.

The component (a1) is at least one di- or polyisocyanate, for example one to four, preferably one to three, particularly preferably one to two and very particularly preferably exactly one.

The monomeric isocyanates are preferably diisocyanates which carry exactly two isocyanate groups. However, it could in principle also be monoisocyanates having an isocyanate group, but these are less preferred.

In principle, higher isocyanates having on average more than 2 isocyanate groups are also suitable, but these are less preferred. Triisocyanates such as triisocyanatononane or 2'-isocyanatoethyl- (2,6-diisocyanatohexanoate) or the mixtures of di-, tri- and higher polyisocyanates are suitable for this purpose.

The monomeric isocyanates have substantially no reaction products of the isocyanate groups with themselves. The monomeric isocyanates are preferably isocyanates having 4 to 20 C atoms. Examples of customary aliphatic diisocyanates are tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate (eg methyl or ethyl 2,6-diisocyanate). diisocyanatohexanoate), trimethylhexane diisocyanate or tetramethylhexane diisocyanate. Examples of cycloaliphatic diisocyanates are 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) cyclohexane or 2,4- or 2,6-diisocyanato-1-methylcyclohexane and 3 (or 4), 8 (or 9) -bis (isocyanatomethyl) -tricyclo [5.2.1.0 ^{2 6} ] decan-isomer mixtures.

Particularly preferred diisocyanates are 1,6-hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and isophorone diisocyanate, very particular preference is given to isophorone diisocyanate and 1,6-hexamethylene diisocyanate, in particular preference to isophorone diisocyanate.

There may also be mixtures of said isocyanates. Isophorone diisocyanate is usually present as a mixture, namely of the cis and trans isomers, generally in the ratio of about 60:40 to 80:20 (w / w), preferably in the ratio of about 70:30 to 75 : 25 and most preferably in the ratio of about 75:25. The content of isomeric compounds in the diisocyanate does not play a decisive role in the process according to the invention. For example, 1,6-hexamethylene diisocyanate may contain a small proportion of 2-urethane (meth) acrylates and / or 3-methyl-1,5-pentamethylene diisocyanate. For the present invention, polyisocyanates can be used both on the basis of such diisocyanates, which is obtained by phosgenation of the corresponding amines, as well as those which are prepared without the use of phosgene, ie by phosgene-free processes. According to EP-A-0 126 299 (US Pat. No. 4,596,678), EP-A-126,300 (US Pat. No. 4,596,679) and EP-A-355 443 (US Pat. No. 5,087,739), it is possible to prepare (cyclo) aliphatic diisocyanates, for example. te, such as 1, 6-hexamethylene diisocyanate (HDI) are prepared by reacting the (cyclo) - aliphatic diamines with, for example, urea and alcohols to (cyclo) aliphatic bis carbamic esters and their thermal cleavage into the corresponding diisocyanates and alcohols. The synthesis is usually carried out continuously in a cyclic process and, if appropriate, in the presence of N-unsubstituted carbamic acid esters, dialkyl carbonates and other by-products recycled from the reaction process. Diisocyanates obtained in this way generally have a very low or even non-measurable proportion of chlorinated compounds, which can lead to favorable color numbers of the products. It is a further advantage of the present invention that the process according to the invention is based on aliphatic diisocyanates and is independent of their preparation, ie irrespective of whether the preparation was effected by means of a phosgenation or a phosgene-free process.

In one embodiment of the present invention, the diisocyanate has a total hydrolyzable chlorine content of less than 200 ppm, preferably less than

120 ppm, more preferably less than 80 ppm, most preferably less than 50 ppm, especially less than 15 ppm and especially less than 10 ppm. This can be measured, for example, by ASTM D4663-98. However, it is of course also possible to use diisocyanates having a higher chlorine content, for example up to 500 ppm. Of course, mixtures of diisocyanate obtained by reacting the corresponding diamine with, for example, urea and alcohols and cleaving the resulting biscarbamic acid ester with such diisocyanate obtained by phosgenation of the corresponding amine can also be used. The polyisocyanates based on these diisocyanates are preferably the following compounds: 1) isocyanurate-containing polyisocyanates of aliphatic and / or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and / or isophorone diisocyanate. The isocyanurates present are, in particular, trisisocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 8.

Uretdione group-containing polyisocyanates having aliphatically and / or cycloaliphatically bonded isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.

The polyisocyanates containing uretdione groups are obtained in the context of this invention in a mixture with other polyisocyanates, in particular those mentioned under 1). For this purpose, the diisocyanates can be reacted under reaction conditions under which both uretdione groups and the other polyisocyanates are formed, or first the uretdione groups formed and these are then reacted to the other polyisocyanates or the diisocyanates first to the other polyisocyanates and these then uretdione-containing Products are implemented.

Urethane and / or allophanate groups containing polyisocyanates having aliphatically or cycloaliphatically bound isocyanate groups, as for example by reacting excess amounts of diisocyanate, for example hexamethylene diisocyanate or isophorone diisocyanate, with monohydric or polyhydric alcohols. These urethane and / or allophanate-containing polyisocyanates generally have an NCO content of 12 to 24 wt .-% and an average NCO functionality of 2.1 to 4.5. Such polyisocyanates containing urethane and / or allophanate groups may be uncatalysed or, preferably, in the presence of catalysts such as, for example, ammonium carboxylates or hydroxides, or allophanatization catalysts, e.g. Zn (II) compounds, in each case in the presence of mono-, di- or polyvalent, preferably monohydric alcohols produced. The urethane and / or allophanate groups containing polyisocyanates may also be prepared in admixture with other polyisocyanates, in particular those mentioned under 1). 4) Uretonimine-modified polyisocyanates.

5) carbodiimide-modified polyisocyanates. 6) Hyperbranched polyisocyanates, as are known, for example, from DE-A1 10013186 or DE-A1 10013187.

7) polyurethane-polyisocyanate prepolymers, of di- and / or polyisocyanates with alcohols.

8) polyurea-polyisocyanate prepolymers.

9) Hydrophilic modified polyisocyanates, i. Polyisocyanates which, in addition to the groups described under 1-10, contain those which formally arise by addition of molecules with NCO-reactive groups and hydrophilicizing groups to the isocyanate groups of the above molecules. The latter are nonionic groups such as alkyl polyethylene oxide and / or ionic, which are derived for example from phosphoric acid, phosphonic acid, sulfuric acid or sulfonic acid, or their salts.

10) polyisocyanates containing iminooxadiazinedione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such polyisocyanates containing iminooxadiazinedione groups can be prepared from diisocyanates by means of special catalysts.

In preferred compounds (a1), the polyisocyanate contains at least one moiety selected from the group consisting of isocyanurates, biurets and allophanates, preferably from the group consisting of isocyanurates and allophanates, as described in WO 00/39183, which is hereby incorporated by reference This disclosure is particularly preferably an isocyanurate group-containing polyisocyanate.

In a particularly preferred embodiment, the polyisocyanate (a1) is a polyisocyanate based on 1,6-hexamethylene diisocyanate and / or isophorone diisocyanate, most preferably based on isophorone diisocyanate.

In particular, the compound (a1) is an isocyanurate group-containing polyisocyanate based on isophorone diisocyanate.

Components (a2)

Components (a2) each comprise at least one, for example one to three, preferably one to two and very particularly preferably exactly one compound having at least one, preferably exactly one isocyanate group-reactive group and at least one

(Meth) acrylate.

Preferred compounds of components (a2) are, for. As the esters of dihydric or polyhydric alcohols with acrylic acid or methacrylic acid, particularly preferably acrylic acid. Suitable alcohols are, for. B. diols such as ethylene glycol, 1, 2-propanediol, 1, 3-propanediol,

1, 1-dimethylethane-1, 2-diol, 2-butyl-2-ethyl-1, 3-propanediol, 2-ethyl-1,3-propanediol,

2-Methyl-1,3-propanediol, neopentyl glycol, neopentyl glycol hydroxypivalate, 1,2,3,1- or 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, bis- (4-hydroxycyclohexane ) isopropylidene, tetramethylcyclobutanediol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, cyclooctanediol, norbornanediol, pinanediol, decalin diol, 2-ethyl-1,3-hexanediol, 2,4-di-ethyl -Octane-1, 3-diol, hydroquinone, bisphenol A, bisphenol F, bisphenol B, bisphenol S, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1, 1, 2, 1, 3 - And 1, 4-cyclohexanedimethanol, 1, 2, 1, 3 or 1, 4-cyclohexanediol, tricyclodecanimethanol.

Suitable triols and polyols have z. B. 3 to 25, preferably 3 to 18 carbon atoms. These include z. Trimethylolpropane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, ditrimethylolpropane, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol), maltitol or isomalt ,

Preferably, the compounds of components (a2) are selected from 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6 Hydroxyhexylacrylate, 6-hydroxyhexylmethacrylate, 3-hydroxy-2-ethylhexylacrylate,

3-hydroxy-2-ethylhexyl methacrylate, trimethylolpropane mono- or diacrylate, pentaerythritol di- or triacrylate, dipentaerythritol pentaacrylate, and mixtures thereof.

Particularly preferred compounds (a2) are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

Components a3) The optional components a3) are at least one compound having at least two, for example two to six, preferably two to four, particularly preferably two to three and very particularly preferably exactly two isocyanate-reactive groups which are selected from Hydroxy, mercapto, primary and / or secondary amino groups, preferably hydroxy and primary amino groups, more preferably hydroxy groups.

Low molecular weight alcohols a3) have a molecular weight of not more than 500 g / mol. Particularly preferred are alcohols having 2 to 20 carbon atoms and, for example, 2 to 6 hydroxyl groups, preferably 2 to 4, more preferably 2 to 3, and most preferably exactly 2 hydroxy groups. Preference is given in particular to hydrolysis-stable short-chain diols having 4 to 20, preferably 6 to 12, carbon atoms. These preferably include 1, 1, 1, 2, 1, 3 or 1, 4-di (hydroxymethyl) cyclohexane, 2,2-bis (4'-hydroxycyclohexyl) propane, 1, 2, 1, 3 or 1, 4-Cy clohexanediol, tetramethylcyclobutanediol, cyclooctanediol or norbornanediol. Particular preference is given to using aliphatic hydrocarbon diols, such as the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols and dodecanediols. Particularly preferred are 1, 2-, 1, 3- or 1, 4-butanediol, 1, 4-pentanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2,5-hexanediol, di (hydroxymethyl) cyclohexane Isomers and 2,2-bis (4'-hydroxycyclohexyl) propane. Most preferably, the diols (a3) are cycloaliphatic diols, in particular 1, 1, 1, 2, 1, 3 or 1, 4-di (hydroxymethyl) cyclohexane, 2,2-bis (4'-hydroxycyclohexyl) propane, 1, 2, 1, 3 or 1, 4-cyclohexanediol. Components a4)

Suitable compounds a4) are also polymeric polyols. Preferably, the number average molecular weight M _{n of} these polymers is in a range of more than 500 to 100,000, particularly preferably 500 to 10,000. The OH numbers are preferably in a range of about 20 to 300 mg KOH / g polymer.

The functionality of the polyols a4) is at least two, for example two to six, preferably two to four, more preferably two to three and most preferably exactly two.

Preferred compounds a4) are polyesterols, polyetherols and polycarbonate polyols, particularly preferably polyesterols and polyetherols and very particularly preferably polyesterols.

Preferred polyesterols are those based on aliphatic, cycloaliphatic and / or aromatic di-, tri- and / or polycarboxylic acids with di-, tri- and / or polyols as well as lactone-based polyesterols.

Polyester polyols are e.g. from Ullmann's Encyclopedia of Industrial Chemistry,

4th edition, Volume 19, pp. 62 to 65 known. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols. The polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally, e.g. by halogen atoms, substituted and / or unsaturated. Examples include:

Oxalic, maleic, fumaric, succinic, glutaric, adipic, sebacic, dodecanedioic, o-phthalic, isophthalic, terephthalic, trimellitic, azelaic, 1,4-cyclohexanedicarboxylic or tetrahydrophthalic, suberic, azelaic,

Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, Maleic anhydride, dimer fatty acids, their isomers and hydrogenation products, and esterifiable derivatives such as anhydrides or dialkyl esters, for example C 1 -C 4 -alkyl esters, preferably methyl, ethyl or n-butyl esters, of the acids mentioned are used. Preference is given to dicarboxylic acids of the general formula HOOC- (CH 2) _y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.

Suitable polyhydric alcohols for preparing the polyesterols are 1, 2-propanediol, ethylene glycol, 2,2-dimethyl-1,2-ethanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-Bu- tandiol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1, 3-diol, 2,4-diethyloctane-1, 3-diol, 1, 6-hexanediol, poly-THF with one molecular weight between 162 and 2000, poly-1,3-propanediol with a molecular weight between 134 and 2000, poly-1,2-propanediol with a molecular weight between 134 and 2000, polyethylene glycol with a molecular weight between 106 and 2000, neopentyl glycol, hydroxypivalin acid neopentyl glycol ester, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1, 1, 2, 1, 3 and 1,4-cyclohexanedimethanol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, trimethylolbutane, trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threit , Erythritol, adonite (ribite), arabitol (lyxite), xyli t, dulcitol (galactitol), maltitol or isomalt, which may optionally be alkoxylated as described above.

Alcohols of the general formula HO- (CH 2) x -OH are preferred, where x is a number from 1 to 20, preferably an even number 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. Further preferred is neopentyl glycol.

Also suitable are polycarbonate diols, as can be obtained, for example, by reacting phosgene with an excess of the low molecular weight alcohols mentioned as synthesis components for the polyesterpolyols. Also suitable are lactone-based polyesterdiols, which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules. Preferred lactones are those which are derived from compounds of the general formula HO- (CH 2) z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit is also denoted by a d- to C ₄ - Alkyl radical may be substituted. Examples are ε-caprolactone, ß-propiolactone, gamma-butyrolactone and / or methyl-e-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone and mixtures thereof. Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols. The corresponding polymers of the ε-caprolactone are particularly preferred. Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers. Instead of the polymers of Lactones can also be the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones, are used.

Preferably, the lactone-based polyesterol is a polycaprolactone diol, which is formally an adduct of caprolactone with a diol HO-R-OH, having the formula

HO - [- CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ - (CO) -O] n R -OH or

HO - [- CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ - (CO) -O] ni-R - [- O- (CO) -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -] wherein n, n1 and n2 are positive integers, for which n = 1 to 5 and (n1 + n2) = 1 to 5 and R is a divalent aliphatic or cycloaliphatic radical having at least one carbon atom, preferably 2 to 20, particularly preferably 2 to 10, most preferably 3 to 6 carbon atoms.

Aliphatic radicals R are, for example, linear or branched alkylene, e.g. Methylene, 1, 2-ethylene, 1, 2 or 1, 3-propylene, 1, 2, 1, 3 or 1, 4-butylene, 1, 1-dimethyl-1, 2-ethylene or 1, 2 -Dimethyl-1, 2-ethylene, 1, 5-pentylene, 1, 6-hexylene, 1, 8-octylene, 1, 10-decylene, or 1, 12-dodecylene. Preference is given to 1,2-ethylene, 1,2- or 1,3-propylene, 1,4-butylene and 1,5-pentylene, more preferably 1,4-butylene and 1,6-hexylene.

Conceivable, albeit less preferred, are cycloaliphatic radicals, for example cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene and cyclododecylene.

Preferred polyesterols as compounds (a4) have a functionality of free hydroxyl groups of at least 2, particularly preferably from 2 to 6, very particularly preferably from 2 to 4, in particular from 2 to 3 and especially of exactly 2.

The molecular weights M _{n of} the polyesterols are preferably between 500 and 4000 (M _n determined by gel permeation chromatography using polystyrene as standard and tetrahydrofuran as eluent). Components (a5) The at least one, for example one to four, preferably one to three, particularly preferably one to two and very particularly preferably exactly one compound (a5) has at least one, for example one to three and preferably one to two isocyanate-reactive group and at least one, for example one to four, preferably one to three, particularly preferably one to two and very particularly preferably exactly one quaternary ammonium group. Particularly preferred compounds (a5) are those of the formula (II)

RR ² R ³ N ⁺ - R ⁴ - Y wherein

R ¹ to R ^{4 have} the meanings given above, and

Y represents an isocyanate-reactive group, preferably a -OH or -Nh group. Preferred compounds (a5) having an isocyanate-reactive group are 2- [N, N-bis (tridecyl) -N-methyl-ammonium]] ethanol, 2- [N, N-bis (hexyl) -N-methyl-ammonium )] ethanol, 2- [N, N-bis (tridecyl) -N-methyl-ammonium)] propan-1-ol, 2- [N, N-bis (hexyl) -N-methyl-ammonium)] propane 1 -ol, N-alkylated Ν, Ν-dimethyl ethanolamine and N-alkylated Ν, Ν-dimethyl propanola- mine, in which the alkyl group preferably at least 6, more preferably at least 8 and most preferably at least 12 carbon atoms. Furthermore, the further one to fifty times, preferably two to thirty times and particularly preferably four to twenty times with ethylene oxide and / or propylene oxide, preferably reacted with ethylene oxide products of such compounds are preferred. Preferred compounds (a5) having two isocyanate-reactive groups are bis (2-hydroxyethyl) alkyl methyl ammonium salts, bis (2-hydroxypropyl) alkyl methyl ammonium salts, bis (2-hydroxyethyl) alkyl benzyl ammonium salts and bis (2-hydroxypropyl) alkyl benzyl ammonium salts in which the alkyl radical preferably comprises at least 6, more preferably at least 8, and most preferably at least 12 carbon atoms. Furthermore, the further one to fifty times, preferably two to thirty times and particularly preferably four to twenty times with ethylene oxide and / or propylene oxide, preferably reacted with ethylene oxide products of such compounds are preferred.

Possible counterions of the ammonium salts are halides, for example chloride, bromide or iodide, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, sulfonate, hydrogensulfonate, methyl sulfonate, tosylate, mesylate, phosphate, hydrogen phosphate, dihydrogen phosphate, carbonate, bicarbonate, methyl carbonate, ethyl carbonate and butyl carbonate.

It is a possible embodiment that the ammonium compound is not bound to the polyurethane according to the invention via a compound of the formula (II) but via a compound (a5a) which contains at least one, for example one to three, preferably one to two and particularly preferably exactly one isocyanate-reactive group and a first wherein the attachment of the ammonium group by further reaction with a compound (a5b) takes place, which is a complementary to the first reactive group complementary reactive group and at least one, for example one to four, preferably one to three, particularly preferably one to two and very particularly preferably has exactly one quaternary ammonium group.

Examples of such first reactive groups and complementary additional reactive groups are as follows:

Among these combinations, it is preferable that both the compound (a5a) and the compound (a5b) carry the same or different alkoxysilyl groups.

In this case, it is generally sufficient if a silyl group is substituted by at least one alkoxy radical, for example one to three, preferably two or three and very particularly preferably three.

These are preferably tris (alkyloxy) silyl groups or alkyl

bis (alkyloxy) silyl groups, particularly preferably tris (C 1 -C 4 -alkyloxy) silyl groups or C 1 -C 4 -alkyl to (C 1 -C 4 -alkyloxy) silyl groups.

Particular preference is given to diethoxymethylsilyl, dimethoxymethylsilyl, methoxydimethylsilyl, ethoxydimethylsilyl, phenoxydimethylsilyl, triethoxysilyl or trimethoxysilyl groups.

Most preferably, the compound (a5a) satisfies the formula (III)

(R ⁵ O) ₃ Si - R ⁶ - Y, in which

Y has the above meaning,

R ^{5 is} C 1 -C 6 -alkyl, preferably C 1 -C ₄ -alkyl, particularly preferably methyl, ethyl, n-propyl, tert-butyl and n-butyl, very particularly preferably methyl, ethyl and n-butyl and in particular methyl and R ^{6 is} a 1 to 10, preferably 2 to 6, particularly preferably 2 to 4 carbon atoms containing divalent hydrocarbon radical

mean.

Preferred compounds (a5a) are 3-aminopropyl siloxanes and 2-aminoethyl siloxanes, particular preference is given to 3-aminopropyltriethoxysilane.

The reaction is then preferably carried out with compounds (a5b) of the formula (IV)

RR ² R ³ N ⁺ - R ⁴ - Si (OR ⁷ ) ₃

wherein

R ¹ to R ^{4 have} the above meanings and

R ^{7 is} C 1 -C 6 -alkyl, preferably C 1 -C 4 -alkyl, particularly preferably methyl, ethyl, n-propyl, tert-butyl and n-butyl, very particularly preferably methyl, ethyl and n-butyl and in particular methyl

means.

Preferred compounds (a5b) are 3-ammonium propyl siloxanes and 2-ammonium ethyl siloxanes, wherein the ammonium groups are each as defined above.

It is possible to prepare the urethane (meth) acrylates according to the invention in such a way that first the compound (a5a) is incorporated and the compound thus obtained is subsequently reacted with the compound (a5b), but the preparation can also be carried out in such a way that simultaneous incorporation the compounds (a5a) and (a5b) are in the urethane (meth) acrylates. The latter is less preferred.

The construction of the urethane (meth) acrylate according to the invention with compounds (a5), however, is preferred over the structure with the compounds (a5a) and (a5b). Components (a6)

In the urethane (meth) acrylates according to the invention, at least one further compound having exactly one isocyanate-reactive group may be used as optional components (a6). This group may be a hydroxy, mercapto, or a primary or secondary amino group. Suitable compounds (a6) are the customary compounds known to the person skilled in the art, which are usually used as so-called terminators for reducing the number of reactive free isocyanate groups or for modifying the polyurethane properties in polyurethane production. These include z. For example, monofunctional alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, etc. Suitable components (a6) are also amines having a primary or secondary amino group, such as. Methylamine, ethylamine, n-propylamine, diisopropylamine, dimethylamine, diethylamine, di- n-propylamine, diisopropylamine, etc.

The urethane (meth) acrylates (A) according to the invention are generally composed per 100 mol% of reactive isocyanate groups in (a1) (in total) as follows:

(a2) 30 to 95 mol%, preferably 40 to 92 mol%, particularly preferably 50 to 90 mol%, very particularly preferably 60 to 80 mol% and in particular 70 to 80 mol%, (a3) 0 to 30 mol%, preferably 0 to 25 mol%, particularly preferably 0 to 20 mol%, very particularly preferably 0 to 15 mol%, in particular 0 to 10 mol% and especially 0%, (a4) 0 to 10 mol%, preferably 0 to 8 mol%, particularly preferably 0 to 5 mol%, very particularly preferably 0 to 3 mol% and in particular 0 mol%, (a5) 5 to 30 mol%, preferably 8 to 25 mol%, particularly preferably 10 to 20 mol%, very particularly preferably 15 to 20 mol% and in particular 18 to 20 mol%,

(a6) up to 10 mol%, preferably up to 8 mol%, particularly preferably up to 5 mol%, very particularly preferably up to 2 mol% and in particular 0 mol%, in each case based on the isocyanate-reactive groups, with the proviso in that the sum of all isocyanate-reactive groups is 80 to 125 mol% of the reactive isocyanate groups in (a1) (in total), preferably 85 to 15 mol%, particularly preferably 90 to 110 mol%, very particularly preferably 95 to 105 mol% and especially 100 mol%.

To prepare the polyurethanes of the invention, the starting components (a1) to (a6), if used, at temperatures of 40 to 180 ° C, preferably 50 to 150 ° C, while maintaining the above NCO / OH equivalent ratio reacted with each other.

The reaction generally takes place until the desired NCO number according to DIN 53185 has been reached.

The reaction time is generally 10 minutes to 12 hours, preferably 15 minutes to 10 hours, more preferably 20 minutes to 8 hours and most preferably 1 to 8 hours. To accelerate the reaction, suitable catalysts may optionally be used. The formation of the adduct of isocyanate group-containing compound and the compound containing isocyanate-reactive groups is generally carried out by mixing the components in any order, optionally at elevated temperature. In this case, the compound containing isocyanate-reactive groups is preferably added to the compound containing isocyanate groups, particularly preferably in several steps.

The isocyanate group-containing compound is particularly preferably initially introduced and the compounds which contain isocyanate-reactive groups are added. In particular, first the isocyanate group-containing compound (a1) is initially charged, then (a2) and then (a5) added or preferably first the isocyanate group-containing compound (a1) presented, then (a5) and then added (a2). Subsequently, optionally desired further components can be added.

Of course, (a2) and (a5) may also be added in admixture with each other.

Components (B) and (C) The mixture of the urethane (meth) acrylate (A) according to the invention contains at least one hydrophilic reactive diluent (B) and optionally at least one further reactive diluent (C) other than (B).

Compounds (B) and (C) are those usually used as reactive diluents. These include z. For example, the reactive diluents as described in P.K.T. Oldring (Editor),

Chemistry & Technology of UV & EB Formulations for Coatings, Inks & Paints, Vol. II, Chapter III: Reactive Diluents for UV & EB Curable Formulations, Wiley and SITA Technology, London 1997. Reactive diluents are, for example, esters of (meth) acrylic acid with alcohols having from 1 to 20 carbon atoms, e.g. (Meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester,

(Meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, dihydrodicyclopentadienyl acrylate. Compounds having at least two free-radically polymerizable C =C double bonds: These include in particular the diesters and polyesters of the abovementioned α, β-ethylenically unsaturated mono- and / or dicarboxylic acids with diols or polyols. Particular preference is given to hexanediol diacrylate, hexanediol dimethacrylate, octanediol diacrylate, octanediol dimethacrylate, nonanedioldiacrylate, nonanediol dimethacrylate, decanediol diacrylate, decanediol dimethacrylate, pentaerythritol diacrylate, dipentaerythritol tetraacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, etc. The esters of alkoxylated polyols with α, β-ethylenically unsaturated are also preferred Mono- and / or dicarboxylic acids such. For example, the polyacrylates or methacrylates of alkoxylated trimer methylolpropane, glycerol or pentaerythritol. Also suitable are the esters of alicyclic diols, such as cyclohexanediol di (meth) acrylate and bis (hydroxymethyl-ethyl) cyclohexane-di (meth) acrylate. Further suitable reactive diluents are trimethylolpropane mono-formal acrylate, glycerol maleate, 4-tetrahydropyranyl acrylate, 2-tetrahydropyranyl methacrylate and tetrahydrofurfuryl acrylate.

Other suitable reactive diluents are, for example, polyether (meth) acrylates.

Polyether (meth) acrylates are preferably (meth) acrylates of one to twenty times and more preferably three to ten times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol ,

In addition, one to twenty times and more preferably three to ten times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated glycerol can be used.

Preferred multifunctional, polymerizable compounds are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate,

1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, polyester polyol acrylates, polyetherol acrylates and triacrylate of one to twenty times alkoxylated, more preferably ethoxylated trimethylolpropane.

Polyether (meth) acrylates may further comprise (meth) acrylates of poly-THF having a molecular weight between 162 and 2000, poly-1,3-propanediol having a molecular weight between 134 and 2,000, or polyethylene glycol having a molecular weight between 238 and 2,000.

The compound (B) present according to the invention is a hydrophilic reactive diluent, the term "hydrophilic" in the context of this document being understood to have a calculated log P value of not more than 1.0, the calculation the log P values are performed with the program ACD / PhysChem Suite, version 12.01 of Advanced Chemistry Development, Inc. (ACD / Labs, Ontario, Canada). The structures of the compounds to be calculated are entered in two dimensions. Preferred hydrophilic reactive diluents (B) derive their hydrophilic property from functional groups other than acid groups.

Acid groups are free carboxy groups (-COOH), sulfonic acid groups (-SO3H), sulfinic acid groups (-SO2H), phosphonic acid groups (-PO (OH) 2), phosphinic acid groups

(> PO (OH)), as well as partially esterified sulfuric acids and phosphoric acids carrying groups (-OSO3H) or (-OPO (OH) ₂ ). Thus, preferred reactive diluents are α, β-unsaturated carboxylic acids, sulfonic acids and phosphonic acids, in particular methacrylic acid, ethacrylic acid, maleic acid including its anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, vinylacetic acid, allylacetic acid, crotonic acid, vinylsulfonic acid and vinylphosphonic acid.

The compounds (B) are preferably selected from the group consisting of hydroxyalkyl (meth) acrylates, N-vinyllactams, particularly preferably hydroxyalkyl (meth) acrylates. Hydroxyalkyl (meth) acrylates as compounds (B) are preferably ω-hydroxyalkyl (meth) acrylates or ((j0-1) -hydroxyalkyl (meth) acrylates, preferably ω-hydroxyalkyl (meth) acrylates.

Particularly preferred hydroxyalkyl (meth) acrylates (B) are those of the formula

H ₂ C = C (R ⁹ ) COO-R ⁸ -OH, wherein R ^{9 is} hydrogen or methyl, preferably hydrogen and

R ^{8 is} a 2 to 10, preferably 2 to 6, more preferably 2 to 4 carbon atoms having divalent hydrocarbon radical.

Preferred radicals R ⁸ are, for example, linear or branched alkylene, for example 1, 2-ethylene, 1, 2 or 1, 3-propylene, 1, 2, 1, 3 or 1, 4-butylene, 1, 1-dimethyl -1, 2-ethylene or 1, 2-dimethyl-1, 2-ethylene, 1, 5-pentylene, 1, 6-hexylene, 1, 8-octylene, 1, 10-decylene, or 1, 12-dodecylene. Preferred are 1, 2-ethylene, 1, 2 or 1, 3-propylene, 1, 4-butylene and 1, 6-hexylene, more preferably 1, 2-ethylene, 1, 2 or 1, 3 Propylene, most preferably 1, 2-ethylene and 1, 2-propylene and in particular 1, 2-ethylene.

The compound (B) is preferably 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate or 4-hydroxybutyl acrylate, particularly preferably 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2- Hydroxypropyl methacrylate or 2-hydroxyethyl methacrylate, and most preferably 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate or 2-hydroxyethyl methacrylate. N-vinyllactams as compounds (B) are preferably N-involuted lactams with five to twelve ring systems, preferably five to ten membered ring systems, particularly preferably five to seven membered ring systems. Preferred N-vinyl lactams are those of the formula

wherein

R ^{10 is} a 2 to 10, preferably 2 to 6, particularly preferably 3 to 5 carbon atoms having divalent hydrocarbon radical

means.

Preferred radicals R ¹¹ are, for example, linear or branched alkylene, for example 1, 2-ethylene, 1, 2 or 1, 3-propylene, 1, 2, 1, 3 or 1, 4-butylene, 1, 1-dimethyl -1, 2-ethylene or 1,2-dimethyl-1,2-ethylene, 1,5-pentylene, 1,6-hexylene, 1,8-octylene or 1,10-decylene. Preference is given to 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,5-hexylene and 1,6-hexylene, more preferably 1,3-propylene, 1,4-butylene and 1,5 -Pentylene, most preferably 1, 3-propylene and 1, 5-pentylene.

Preferred N-vinyllactams as compounds (B) are N-vinylpyrrolidone or N-vinylcaprolactam.

The compound (B) may be a single compound or a mixture of several, for example up to four, preferably up to three compounds, more preferably one or two compounds and most preferably exactly one compound.

Optionally, at least one reactive diluent (C) may be present, which is not a hydrophilic reactive diluent, that is, other than the reactive diluent (B), preferably has a logP value of more than 1.

Particularly preferred compounds (C) are multifunctional (meth) acrylates, ie those having a functionality of at least 2, for example 2 to 10, preferably 2 to 6, more preferably 2 to 5 and most preferably 2 to 4.

Compound (C), as they are usually used as reactive diluents, are known per se to the person skilled in the art. These include z. For example, the reactive diluents as described in P.K.T. Oldring (Editor), Chemistry & Technology of UV & EB Formulations for Coatings, Inks & Paints, Vol. II, Chapter III: Reactive Diluents for UV & EB Curable Formulations, Wiley and SITA Technology, London 1997.

Compounds having at least two free-radically polymerizable C =C double bonds: These include in particular the diesters and polyesters of (meth) acrylic acid with diols or polyols. Particular preference is given to 1,4-butanediol di (meth) acrylate, 1,6-hexanediol diacrylate, hexanediol dimethacrylate, octanediol diacrylate, octanediol dimethacrylate, nonanediol diacrylate, nonanediol dimethacrylate, decanediol diacrylate, decanediol dimethacrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, pentaerythritol diacrylate, dipentaerythritol tetraacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, etc.

Also preferred are the esters of alkoxylated polyols, with (meth) acrylic acid, such as. B. the polyacrylates or methacrylates of each OH group on average one to ten times, preferably one to five times, particularly preferably one to three times and very particularly preferably one to two times alkoxylated, for example ethoxylated and / or propoxylated, preferably ethoxylated or propoxylated and particularly preferably exclusively ethoxylated trimethylolpropane, glycerol or pentaerythritol. Also suitable are the esters of alicyclic diols, such as cyclohexanediol di (meth) acrylate and bis (hydroxymethyl-ethyl) cyclohexane-di (meth) acrylate.

Further suitable reactive diluents are, for example, urethane (meth) acrylates, epoxy (meth) acrylates, polyether (meth) acrylates, polyester (meth) acrylates or polycarbonate (meth) acrylates.

acrylate urethane (meth)

Urethane (meth) acrylates are e.g. obtainable by reacting polyisocyanates with hydroxyalkyl (meth) acrylates or vinyl ethers and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols.

Such urethane (meth) acrylates contain as structural components essentially:

(1) at least one organic aliphatic, aromatic or cycloaliphatic di- or polyisocyanate,

(2) at least one compound having at least one isocyanate-reactive group and at least one radically-polymerizable unsaturated group, and

(3) optionally at least one compound having at least two isocyanate-reactive groups.

The urethane (meth) acrylates preferably have a number average molecular weight M _n of 500 to 20,000, in particular of 500 to 10,000, more preferably 600 to 3000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).

The urethane (meth) acrylates preferably have a content of 1 to 5, particularly preferably 2 to 4 moles of (meth) acrylic groups per 1000 g of urethane (meth) acrylate. Particularly preferred urethane (meth) acrylates have an average functionality of 1.5 to 4.5. acrylates epoxy (meth)

Epoxide (meth) acrylates are preferably obtainable by reacting epoxides with (meth) acrylic acid. Suitable epoxides are, for example, epoxidized olefins, aromatic glycidyl ethers or aliphatic glycidyl ethers, preferably those of aromatic or aliphatic glycidyl ethers.

Epoxidized olefins may be, for example, ethylene oxide, propylene oxide, isobutylene oxide, 1-butoxide, 2-butene oxide, vinyl oxirane, styrene oxide or epichlorohydrin. Preferred are ethylene oxide, propylene oxide, iso-butylene oxide, vinyl oxirane, styrene oxide or epichlorohydrin, more preferably ethylene oxide , Propylene oxide or epichlorohydrin and most preferably ethylene oxide and epichlorohydrin.

Aromatic glycidyl ethers are e.g. Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, alkylation products of phenol / dicyclopentadiene, e.g. 2,5-bis [(2,3-epoxypropoxy) phenyl] octahydro-4,7-methano-5H-indene (CAS # [13446-85-0]), tris [4- (2,3-) epoxypropoxy) phenyl] methane isomers) CAS-No. [66072-39-7]), phenol-based epoxy novolacs (CAS No. [9003-35-4]), and cresol-based epoxy novolacs (CAS No. [37382-79-9]). Preference is given to bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, bisphenol A diglycidyl ether being particularly preferred.

Aliphatic glycidyl ethers are, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,1,2,2-tetrakis [4- (2,3-epoxypropoxy) phenyl] ethane (CAS No. [ 27043-37-4]), diglycidyl ethers of polypropylene glycol (a, (jo-bis (2,3-epoxypropoxy) poly (oxypropylene) (CAS No. [16096-30-3]) and of hydrogenated bisphenol A (2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, CAS No. [13410-58-7]).

Preference is given to 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether and 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane.

Particularly preferred are the above-mentioned aromatic glycidyl ethers. The epoxy (meth) acrylates and vinyl ethers preferably have a number average molecular weight Mn of from 200 to 20,000, particularly preferably from 200 to 10,000 g / mol and very particularly preferably from 250 to 3,000 g / mol; the content of (meth) acrylic or vinyl ether groups is preferably 1 to 5, particularly preferably 2 to 4, per 1000 g of epoxy (meth) acrylate or vinyl ether epoxide (determined by gel permeation chromatography using polystyrene as standard and tetrahydrofuran as eluent). Preferred epoxide (meth) acrylates have an OH number of 40 to 400 mg KOH / g.

Preferred epoxide (meth) acrylates have an average OH functionality of 1.5 to 4.5.

Particularly preferred epoxy (meth) acrylates are those which are obtained from processes according to EP-A-54 105, DE-A 33 16 593, EP-A 680 985 and US Pat

EP-A-279 303, in which a (meth) acrylic ester is prepared from (meth) acrylic acid and hydroxy compounds in a first stage and excess in a second stage

(Meth) acrylic acid is reacted with epoxides. Polyester (meth) acrylates

As polyester (meth) acrylates are at least partially or preferably completely

(meth) acrylated reaction products of such polyesterols as listed above under the compounds a4).

Carbonate (meth) acrylates

On average, carbonate (meth) acrylates preferably contain 1 to 5, in particular 2 to 4, particularly preferably 2 to 3 (meth) acrylic groups and very particularly preferably 2 (meth) acrylic groups.

The number average molecular weight M _{n of} the carbonate (meth) acrylates is preferably less than 3000 g / mol, more preferably less than 1500 g / mol, more preferably less than 800 g / mol (determined by gel permeation chromatography with polystyrene as standard, solvent tetrahydrofuran).

The carbonate (meth) acrylates can be obtained in a simple manner by transesterification of carbonic acid esters with polyhydric, preferably dihydric alcohols (diols, eg hexanediol) and subsequent esterification of the free OH groups with (meth) acrylic acid or else transesterification with (meth) acrylic acid esters, as eg in EP-A 92,269. They are also available by reacting phosgene, urea derivatives with polyvalent, e.g. dihydric alcohols.

Also conceivable are (meth) acrylates or vinyl ethers of polycarbonate polyols, such as the reaction product of one of the abovementioned diols or polyols and a carbonic acid ester and also a (meth) acrylate or vinyl ether containing hydroxyl groups. Suitable carbonic acid esters are, for example, ethylene, 1, 2 or 1, 3-propylene carbonate, carbonic acid dimethyl, diethyl or dibutyl ester.

Suitable hydroxyl-containing (meth) acrylates are, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate and pentaerythritol mono-, di- and tri (meth) acrylate.

Suitable hydroxyl-containing vinyl ethers are e.g. 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether.

Particularly preferred carbonate (meth) acrylates are those of the formula:

wherein R is H or CH3, X is a C2-C18 alkylene group and n is an integer from 1 to 5, preferably 1 to 3.

R is preferably H and X is preferably C 2 - to C 10 -alkylene, for example 1, 2-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 4-butylene or 1, 6-hexylene, more preferably for C ₄ - to Ce-alkylene. Most preferably, X is for

Ce alkylene.

The carbonate (meth) acrylates are preferably aliphatic carbonates (meth) acrylates.

These also include conventional, known in the art polycarbonates with terminal hydroxyl groups, z. B. by reacting the aforementioned diols with phosgene or carbonic diesters are available.

Polyether (meth) acrylates

Polyether (meth) acrylates are preferably (meth) acrylates of one to twenty times and more preferably three to ten times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol , In addition, one to twenty times and more preferably three to ten times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated glycerol can be used. Preferred multifunctional, polymerizable compounds are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate,

Polyether (meth) acrylates may also be (meth) acrylates of polyTHF having a molecular weight between 162 and 2000, poly-1,3-propanediol having a molecular weight between 134 and 2,000, or polyethylene glycol having a molecular weight between 238 and 2,000. In a preferred embodiment of the present invention, no compound (C) is present.

If the curing of the coatings according to the invention does not take place with electron beams but by means of UV radiation, the preparations according to the invention preferably contain at least one photoinitiator (D) which can initiate the polymerization of ethylenically unsaturated double bonds.

For example, photoinitiators (D) may be photoinitiators known to those skilled in the art, e.g. those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in K.K. Dieterker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P.K.T. Oldring (Eds), SITA Technology Ltd, London.

Suitable photoinitiators as described in WO 2006/005491 A1, page 21, line 18 to page 22, line 2 (corresponding to US 2006/0009589 A1, paragraph [0150]), which are hereby incorporated by reference into the present disclosure be.

Also suitable are non- or slightly yellowing photoinitiators of the phenylglyoxalic ester type, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.

Typical mixtures include, for example, 2-hydroxy-2-methyl-1-phenyl-propan-2-one and 1-hydroxycyclohexyl phenyl ketone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 2-hydroxy 2-methyl-1-phenyl-propan-1-one, benzophenone and 1-hydroxy-cyclohexyl-phenylketone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 1-hydroxycyclohexyl-phenylketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzophenone and 4-methylbenzophenone or 2,4,6-tri- methylbenzophenone and 4-methylbenzophenone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Preferred among these photoinitiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzophenone, 1-hydroxycyclohexyl-phenylketone, 1-benzoylcyclohexane -1 -ol, 2-hydroxy-2,2-dimethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone and mixtures thereof.

The coatings of the invention contain the photoinitiators (D) preferably in an amount of 0.05 to 10 wt .-%, particularly preferably 0.1 to 8 wt .-%, in particular 0.2 to 5 wt .-%, based on the Total amount of the radiation-curable compounds (A) and (B) and optionally (C).

The dispersions according to the invention can be further coating customary additives (E), such as extenders, defoamers, UV absorbers, sterically hindered amines (HALS), plasticizers, anti-settling agents, dyes, pigments, antioxidants, activators (accelerators), antistatic agents , Flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents and / or fillers. The coatings according to the invention can contain from 0 to 10% by weight, based on the sum of the compounds (A) and (B) and optionally (C), of at least one compound (E).

Suitable stabilizers include typical UV absorbers such as oxanilides, triazines, preferably hydroxyphenyltriazine, and benzotriazole (the latter available as Tinuvin® Ciba Specialty Chemicals) and benzophenones.

These may, alone or together with based on the sum of the compounds (A) and (B) and optionally (C) additionally 0 to 5 wt% of suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2 , 6-di-tert-butylpiperidine or their derivatives, for. B. bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate or preferably bis (1, 2,2,6,6-pentamethyl-4-piperidyl) sebacate used.

Furthermore, one or more thermally activatable initiators can be added, for example potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobis / sobutyronitrile, cyclohexylsulfonylacetyl peroxide, di- / sopropyl percarbonate, ferric butyl peroctoate or benzopinacol, and, for example, such thermally activatable initiators, which have a half-life at 80 ° C of more than 100 hours, such as di-t-butyl peroxide, Cumolhyd- roperoxid, dicumyl peroxide, t-butyl perbenzoate, silylated pinacols, the z. B. commercially available under the trade name ADDID 600 from Wacker or hydroxyl-containing amine-N-oxides, such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6- Tetramethylpiperidine N-oxyl etc. Further examples of suitable initiators are described in "Polymer Handbook" 2nd ed., Wiley & Sons, New York.

Suitable thickeners besides free-radically (co) polymerized (co) polymers, customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite are also suitable.

As chelating agents, e.g. Ethylenediamine acetic acid and its salts and ß-diketones can be used. Suitable fillers include silicates, e.g. For example, by hydrolysis of silicon tetrachloride available silicates such as Aerosil R from. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc. Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin R brands of Ciba Specificity chemistry) and benzophenones. These may be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine,

2,6-di-tert-butylpiperidine or derivatives thereof, e.g. For example, bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate be used. Stabilizers are usually used in amounts of 0.1 to

5.0% by weight, based on the "solid" components contained in the preparation. The antimicrobial radiation-curable coatings according to the invention are as a rule composed as follows:

(A) 30 to 80% by weight, preferably 40 to 70% by weight,

(B) 20 to 70% by weight, preferably 30 to 60% by weight,

(C) 0 to 30% by weight, preferably 0 to 20, particularly preferably 0 to 10 and very particularly preferably 0% by weight

(D) 0 to 10, preferably 0.05 to 10% by weight, particularly preferably 0.1 to 8% by weight, in particular 0.2 to 5% by weight,

(E) 0 to 20% by weight, preferably 0 to 10, particularly preferably 0 to 1% by weight, with the proviso that the sum is always 100% by weight.

The coatings according to the invention are particularly suitable for coating substrates such as wood, paper, textile, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, such as cement blocks and fiber cement boards, and in particular of metals or coated metals. Preferably, the coating of steel, especially medical steel, and plastics, in particular acrylonitrile-butadiene-styrene (ABS) and polycarbonate (PC) plastics. With particular advantage, the antimicrobial, radiation-curable coating according to the invention are suitable for coating medical devices and objects, for example, laboratory tables, operating tables, work surfaces and device surfaces. The substrates are coated by customary methods known to those skilled in the art, at least one coating composition in the composition as described above being applied to the substrate to be coated in the desired thickness and any volatile constituents of the coating composition removed. If desired, this process can be repeated once or several times. The application to the substrate can in a known manner, for. B. by spraying, filling, doctoring, brushing, rolling, rolling or pouring done. The coating thickness is generally in a range of about 3 to 1000 g / m ² and preferably 10 to 200 g / m ² .

To remove the volatile constituents contained in the coating composition, it is optionally possible to dry after application to the substrate, for example in a tunnel oven or by flash-off. The drying can also be carried out by NIR radiation, where NIR radiation here electromagnetic radiation in the wavelength range of 760 nm to 2.5μηι, preferably from 900 to 1500 nm is designated.

Optionally, when multiple layers of the coating composition are applied one above the other, radiation curing takes place after each coating operation. The radiation hardening takes place by the action of high-energy radiation, ie

UV radiation or daylight, preferably light of wavelength 250 to 600 nm or by irradiation with high-energy electrons (electron radiation, 150 to 300 keV). The radiation sources used are, for example, high-pressure mercury vapor lamps, lasers, pulsed lamps (flash light), halogen lamps or excimer radiators. The radiation dose usually sufficient for crosslinking upon UV curing is in the range of 80 to 3000 mJ / cm ² .

The irradiation may optionally also in the absence of oxygen, for. B. under inert gas atmosphere, are performed. Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide or combustion gases. Furthermore, the irradiation can be carried out by covering the coating composition with transparent media. Transparent media are z. As plastic films, glass or liquids, eg. B. water. Particular preference is given to irradiation in the manner as described in US Pat

DE-A1 199 57 900 is described. In a preferred method, the curing is carried out continuously by passing the substrate treated with the preparation according to the invention at a constant speed past a radiation source. For this purpose, it is necessary that the curing rate of the preparation according to the invention is sufficiently high. This different chronological course of the curing can be used in particular if the coating of the article still has a processing followed, in which the film surface comes into direct contact with another object or is mechanically processed.

The invention will be further illustrated by the following non-limiting examples.

Examples

Unless otherwise indicated, parts and percentages are by weight.

Determination of antimicrobial activity by fluorescence microscopy 1. Bacterial culture: 50 ml of DSM 92 medium (= TSBY medium, German Collection of Microorganisms and Cell Cultures GmbH) in a baffled Erlenmeyer flask are inoculated with a single colony of Staphylococcus aureus ATCC 6538P and incubated at 190 rpm and 37 ° C. for 16 hours. The resulting preculture has a cell density of approximately 10 ⁸ cfu / mL corresponding to an optical density of OD = 7.0-8.0. With this preculture, 15 ml of main culture are prepared in 5% DSM 92 medium with an optical density of OD = 1.0.

Analogous cultures are prepared for testing

E. coli ATCC = 8739: preculture 100% DSM 1 medium (nutrient medium without agar), main culture 5% DSM 1 medium

- S. faecalis ATCC = 1 1700: preculture 100% DMS 53 medium (Corynebacterium medium without agar), main culture 5% DSM 53 medium

- P. aeruginosa ATCC = 15442 (incubation at 30 ° C): preculture 100% DSM 546 medium (LC medium), main culture 10% DSM 546 medium 2. Fluorescence staining:

500 μΙ_ the main culture bacteria are according to the manufacturer's recommendation with 1, 5 to 9 μΙ_ SY fluorescent dye and 1, 5 μΙ_ propidium iodide fluorescent dye (film Tracer ™ LIVE / DEAD ^® Viability Kit biofilm, Fa. Invitrogen) stained. 10 μΙ_ of this bacterial suspension are placed on the surface to be examined and covered with a coverslip. In this case, an approximately 30 μηη thick homogeneous liquid film is formed. The test substrates are incubated for up to 2 hours at 37 ° C in the dark. After this time,> 95% of living bacterial cells are found on untreated reference substrates (eg pure glass).

3. Microscopy:

The test substrates are examined on a Leica DMI6000 B microscope with the cover glass oriented toward the objective. 15 predefined positions are automatically approached on each test substrate and images in the three channels phase contrast (P), red (R) and green (G) are recorded. taken. The absorbance and emission wavelengths in the fluorescence channels are matched to the dyes used. Bacteria with an intact cell membrane (live) are detected in the green channel, bacteria with a defective cell membrane (dead) are detected in the red channel. The sum of all bacteria is detected in the phase contrast channel. For each of the 15 digits the number of bacteria in all 3 channels is counted. The percentage of dead bacteria is calculated either from the numbers in R / (R + G) or, if in the green channel background fluorescence is observed from R / P. The percentage of dead bacteria is averaged over the 15 digits and output as a result.

Calculation of log P (ow) values:

Log P (ow) values were calculated using the ACD / PhysChem Suite program, version 12.01, from Advanced Chemistry Development, Inc. (ACD / Labs, Ontario, Canada). Preparation of urethane acrylate UA1:

500 parts of a trifunctional isocyanurate based on 1,6-hexamethylene diisocyanate (Basonat® HI 100, BASF SE), 230 parts of hydroxyethyl acrylate, 2 parts of methylhydroquinone and 0.1 part of di-butyltin dilaurate were combined at room temperature and the reaction temperature was controlled for 3 hours Cooling and heating in a range of 80 ° C to 85 ° C. It was diluted with 150 parts of butyl acetate and the temperature was lowered to 50 ° C. Then 16 parts of aminopropyltriethoxysilane were added over 60 minutes and allowed to react for 3 hours. This gave a colorless Urethanacrylatharz with an NCO (isocyanate) value <0.1%.

Preparation of urethane acrylate UA2:

In a three-necked flask with reflux condenser and stirrer were 624.78 g of Laromer ^® LR 9000 (commercial product of BASF SE, allophanate-containing isocyanato based on

1, 6-hexamethylene diisocyanate having an NCO value of 14.5-15.5%, a viscosity according to DIN EN ISO 3219 (shear rate D) at 23 ° C of 1000 to 1400 mPas and a double bond density of about 3.5 mol / kg), 0 , 50 g of methylhydroquinone and 1, 00 g of 2,6-di-tert-butyl-p-cresol mixed at room temperature. 0.20 g of di-butyltin dilaurate were added as catalyst to the well-mixed initial charge. 245.22 g of 3-aminopropyltriethoxysilane were added dropwise to this mixture over the course of 4.5 hours at room temperature. An exothermic reaction was observed, with the internal temperature rising to 45 ° C. At the same time, the viscosity of the reaction mixture increased. Therefore, the addition of 300 g of butyl acetate. The reaction was continued at an internal temperature of 60 ° C. until the NCO value of the reaction mixture was 4.09%. Then 128.50 g of 2-hydroxyethyl acrylate were added dropwise within 25 minutes. The reaction mixture was then stirred for two hours at 75 ° C internal temperature until the NCO value of the reaction mixture was 0.03%. The solids content of the urethane acrylate was 79.7%. The double bond density of the solvent-free urethane acrylate was 2.41 mol / kg.

Preparation of urethane acrylate UA3: 100 parts of a trifunctional isocyanurate (Basonat HI 100, BASF SE), 49 parts of hydroxyethyl acrylate, 0.2 part of methylhydroquinone and 0.05 part of dibutyltin dilaurate were combined at room temperature and the reaction temperature was controlled by cooling and heating in a range for 4 hours from 80 ° C to 85 ° C. The reaction mixture was diluted with 16 parts of butyl acetate and bottled. a) To 10 parts of this reaction mixture was added 2 parts of Tamol® Fix OK (BASF SE, quaternary cationic, oxyethylated oleylamine derivative having the OH number 170) and 0.01 part Phenothiazine within 60 minutes and allowed to 6 hours Continue to react at 60 ° C. Subsequently, 4.3 parts of butanediol monoacrylate were added. This gave a colorless Urethanacrylatharz with an NCO (isocyanate) value <0.1%. b) to 10 parts of this reaction mixture was added 2.8 parts of di- (tridecyl) -hydroxypropyl-methyl ammonium methylsulfat and 0.01 parts of phenothiazine within 60 minutes and allowed to react for 6 hours at 60 ° C. Subsequently, 4.3 parts of butanediol monoacrylate were added. This gave a colorless Urethanacrylatharz with an NCO (isocyanate) value <0.1%.

Examples 1 - 4

100 parts of the urethane acrylate UA1, 25 parts of monofunctional acrylates (reactive diluent) and 10 parts of octadecyl-dimethyl - [(trimethoxysilyl) propyl] -ammonium chloride, 500 (photoinitiator) was added with 2 parts of Irgacure ^®, on slides in a layer thickness of ca. 25 μηη dry film thickness and cured under nitrogen atmosphere with about 1400 mJ / cm ² in an IST exposure system and then thermally cured at 100 ° C for 30 minutes.

Comparative Examples 1-3

100 parts of urethane acrylate UA1, 25 parts of monofunctional acrylates (reactive diluents) and 10 parts of octadecyl-dimethyl (trimethoxysilyl) -propyl-ammonium chloride are mixed with 2 parts Irgacure ^® 500, applied to microscope slides in a thickness of about 25 μηη dry film thickness and Hardened under nitrogen atmosphere with about 1400 mJ / cm ² in an IST exposure system. Compare Log P (ow)% Kill S. aureus JIS Z 2801

ATCC 6538P after 2 log reducing hours (fluorescence microscopy)

1 methyl methacrylate 1, 21 3 ± 2

2 phenoxyethyl acrylate 2.37 1 ± 1

3 Cyclohexyl methacrylate 3.18 6 ± 6 R = 5.2

The antimicrobial activity of Example 3 and Comparative Example 3 against Staphylococcus aureus ATCC 6538P was additionally determined according to the JIS Z2801 standard. In this test both antimicrobials exhibited a high antimicrobial activity> R> 5. This showed that (1) the fluorescence microscopy test described above has a very high threshold (much higher than in JIS Z2801) for the display of antimicrobial activity and thus Contrary to JIS Z2801 it is possible to distinguish between active and extremely high active paints. This showed (2) that the lacquers of Examples 1 -3 have extremely high antimicrobial activity. Example 5:

100 parts of the urethane acrylate UA1, 25 parts of butanediol monoacrylate and is surrounded in Examples 5A-F parts octadecyl-dimethyl- (trimethoxysilyl) propyl ammonium chloride was added with 2 parts of Irgacure ^® 500, on slides in a layer thickness of about 25 μηη Dry film thickness applied and cured under nitrogen atmosphere with about 1400 mJ / cm ² in an IST exposure system.

By Example 5E, the broad spectrum of antimicrobial paints was demonstrated. Example 6 Per 10 parts of the urethane acrylate UA3 a) and b) were mixed with 0.2 part of Irgacure ^® 500, mounted on slides in a layer thickness of about 25 μηη dry film thickness and cured in a IS exposure system under a nitrogen atmosphere with 1400 mJ / cm ² ,

Example 7

Determination of paint hardness (pendulum damping) The determination of the pendulum damping was carried out according to DIN 53157. For this purpose, the radiation-curable compositions with a wet film thickness of 400 μm were applied to glass. The wet films were first flashed off at room temperature for 15 minutes and then dried at 100 ° C. for 20 minutes. The curing of the films obtained in this way was carried out at 100 ° C on an IST coating system (type M 40 2x1 -R-IR-SLC-So inert) with 2 UV lamps (high pressure mercury lamps type M 400 U2H and type M 400 U2HC) and a conveyor belt speed of 10 m / min under a nitrogen atmosphere (content of O2 not more than 500 ppm). The radiation dose was about 1400 mJ / cm ² . In the embodiment a) was cured only by radiation energy, as described above. In embodiment b) was first exposed to UV light as described above, and then thermally end-cured.

Example 5E a): pendulum hardness 22 sec

Example 5E b): 30 min at 100 ° C pendulum hardness: 59 sec

The antimicrobial properties do not change significantly.

The table shows that a subsequent thermal treatment can improve the mechanical properties of the paints (hardness) without significantly impairing the antimicrobial activity. Example 8-12

100 parts of the urethane acrylate UA1, parts of butanediol monoacrylate (BDMA) as shown in Table and 8 parts of octadecyl-dimethyl- (trimethoxysilyl) propyl ammonium chloride was added with 2 parts of Irgacure ^® 500, up on slides in a layer thickness of about 25 μηη dry film thickness and cured in a nitrogen atmosphere at about 1400 mJ / cm ² in an IST exposure system and annealed at 100 ° C for 30 minutes.

Example 13

A mixture of 7 parts of octadecyldimethyl- (trimethoxysilyl) -propyl-ammonium chloride and 7 parts of butanediol monoacrylate with 68 parts of a urethane acrylate prepared by reacting a trifunctional isocyanurate based on 1,6-hexamethylene diisocyanate (Basonat® HI 100, BASF SE) with 2 moles of hydroxyethyl acrylate and 1 mole of aminopropyltriethoxysilane (based on NCO groups), and another 18 parts of produced butanediol monoacrylate and mixed with 2 parts of Irgacure® 500, applied to microscope slides in a thickness of about 25 μηη dry film thickness and under nitrogen atmosphere with about 1400 mJ / cm ² hardened in an IST exposure system. Subsequently, the slides were thermally cured for 30 min at 100 ° C.

Comparative Example 4 to Example 13:

A mixture of 8 parts of octadecyldimethyl- (trimethoxysilyl) -propyl-ammonium chloride and 8 parts of butanediol monoacrylate with 64 parts of a urethane acrylate prepared by reaction of a trifunctional isocyanurate based on 1,6-hexamethylene diisocyanate (Basonat® HI 100, BASF SE) with 2 moles of hydroxyethyl acrylate and 1 mole of aminopropyltriethoxysilane (based on NCO groups), and 18 parts of methacrylic acid and mixed with 2 parts Irgacure® 500, applied to microscope slides in a thickness of about 25 μηη dry film thickness and under nitrogen atmosphere with approx 1400 mJ / cm ² hardened in an IST exposure system. Subsequently, the slides were thermally cured for 30 min at 100 ° C.

Comparative Example 4 shows that methacrylic acid as reactive diluent (B) shows no effect according to the invention.

Claims

claims

1 . Antimicrobial radiation-curable coatings obtained by reaction of

- (A) at least one urethane (meth) acrylate, the

at least one (meth) acrylate group and

contains

(B) at least one hydrophilic reactive diluent,

(C) optionally at least one reactive diluent other than (B),

- (D) optionally at least one photoinitiator and

- (E) optionally at least one further paint additive.

2. Coatings according to claim 1, characterized in that the quaternary ammonium group has the formula (I)

R ¹ R ² R ³ N ⁺ - R ⁴ - wherein

R ¹ , R ² and R ^{3 are} each independently of one another alkyl groups having 1 to 20 carbon atoms, aryl groups having from 6 to 14 carbon atoms or aralkyl groups having from 7 to 20 carbon atoms, where two of the radicals R ¹ to R ^{3 may} also together form part of a ring, and

R ^{4 represents} a 1 to 10 carbon atoms having divalent hydrocarbon radical.

3. Coatings according to claim 2, characterized in that at least one of the radicals R ¹ to R ^{3 has} at least 10 carbon atoms.

4. Coatings according to one of the preceding claims, characterized in that it is a urethane (meth) acrylate in the compound (A), composed of the components

(a1) at least one diisocyanate or polyisocyanate,

(a2) at least one compound having at least one isocyanate-reactive group and at least one (meth) acrylate group,

(a4) optionally at least one high molecular weight compound having at least two isocyanate-reactive groups,

(a5) at least one compound having at least one isocyanate-reactive group and at least one quaternary ammonium group and

GSZ / sm 27.01 .2012 (a6) optionally at least one compound having exactly one isocyanate-reactive group.

Coatings according to Claim 4, characterized in that the component (a5) is formed from a compound (a5a) which has at least one isocyanate-reactive group and a first reactive group by reaction with a compound (a5b), one opposite to the first reactive group has complementary further reactive group and at least one quaternary ammonium group.

Coatings according to claim 4, characterized in that the first reactive group and the complementary further reactive group are silyl groups which are substituted by at least one alkoxy radical.

Coatings according to claim 4, characterized in that the first reactive group is an isocyanate group and the complementary further reactive group is a hydroxy group.

Coatings according to any one of the preceding claims, characterized in that compound (A) has a density of ammonium groups of at least 0.07 mol per 1000g.

Coatings according to one of the preceding claims, characterized in that compound (B) has a calculated log P value of not more than 1.0, the calculation of the log P values using the program ACD / PhysChem Suite, version 12.01 of the company Advanced Chemistry Development, Inc. (ACD / Labs, Ontario, Canada) and Compound (B) carries no acid groups.

0. Coatings according to one of the preceding claims, characterized in that compound (B) is selected from the group consisting of hydroxyalkyl (meth) - acrylates, N-vinyl lactams.

1 . Coatings according to one of the preceding claims, characterized in that compound (B) is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, N-vinylpyrrolidone and N-vinylcaprolactone.

2. Coatings according to one of the preceding claims, characterized in that it is composed as follows:

(A) 30 to 80% by weight

(B) 20 to 70% by weight

(C) 0 to 30% by weight (D) 0 to 10% by weight,

(E) 0 to 20% by weight with the proviso that the sum is always 100% by weight.

3. Use of coatings according to one of the preceding claims for coating wood, paper, textile, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, metals or coated metals.

4. Use of coatings according to one of claims 1 to 12 for coating medical devices and objects.

5. A process for the antimicrobial treatment of substrates, characterized in that applying a coating according to any one of claims 1 to 12 to the substrate, optionally drying and then cured with a high-enough radiation.