WO2013110566A1

WO2013110566A1 - Radiation-curable anti-microbial coating compound

Info

Publication number: WO2013110566A1
Application number: PCT/EP2013/051030
Authority: WO
Inventors: Reinhold Schwalm; Rupert Konradi; Herbert Platsch; Christina Haaf; Catharina Hippius
Original assignee: Basf Se; Basf Schweiz Ag
Priority date: 2012-01-27
Filing date: 2013-01-21
Publication date: 2013-08-01

Abstract

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

Description

Radiation curable antimicrobial coating

Description: The present invention relates to radiation-curable antimicrobial coating compositions, 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 coating compositions 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 coating composition containing

(A) at least one compound having at least one quaternary ammonium group substituted by four radicals having in total at least 12 carbon atoms, of which at least one, preferably two, radicals each have one hydroxy group or one each

Wear alkoxysilane group,

(B) at least one reactive diluent selected from the group consisting of hydroxyalkyl (meth) acrylates and N-vinyllactams,

(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 coating compositions 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 compound (A), are those which contain at least one quaternary ammonium group substituted by four radicals having a total of at least 12 carbon atoms, of which at least one of the radicals in each case a hydroxy group or each carries an alkoxysilane group.

In a preferred embodiment, two of the four radicals have at least eight carbon atoms.

The compounds (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. Compounds (A) are distinguished into those compounds (A1) which have at least one, preferably two, radicals which each carry a hydroxyl group and compounds (A2) which have at least one, preferably two, radicals which each carry an alkoxysilane group. "Quaternary ammonium groups" in the sense of the present specification are those which are substituted by hydrocarbon radicals and spacers having at least one hydroxyl group or alkoxysilane group. The number of carbon atoms in these quaternary ammonium groups is determined from the sum of the carbon atoms in the 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 in the chain.

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.

Preferred compounds (A1) are those having two hydroxy groups. Particular preference is given to bis (2-hydroxyethyl) alkyl methyl ammonium salts, bis (2-hydroxypropyl) alkyl methyl ammonium monium 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 only with ethylene oxide products of such compounds are preferred.

In a preferred embodiment for compounds (A2), 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 1 to 20, preferably one to 15 carbon atoms having alkyl groups, 6 to 14, preferably 6 to 10, particularly preferably 6 carbon atoms Aryl groups or 7 to 20, preferably 7 to 15, particularly preferably 7 to 10 carbon atoms having aralkyl groups, where two of the radicals R ¹ to R ^{3 may} also be part of a ring together, 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) preferably have a density of ammonium groups of at least 0.5 mol per 1000 g, particularly preferably from 0.5 to 3.5 and very particularly preferably from 1.5 to 3 mol per 1000 g.

Components (A2)

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 (A2) has at least one, for example one to three, preferably one to two and particularly preferably exactly one hydroxyl-reactive Group and at least one, for example one to four, preferably one to three, more preferably one to two and most preferably exactly one quaternary ammonium group on.

Particularly preferred compounds (A2) 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 is an alkoxysilane group. Preferred compounds (A2) are octadecyl-dimethyl- [3- (tris-alkyloxysilyl) -propyl] -ammonium, octadecyl-dimethyl- [2- (tris-alkyloxysilyl) -ethyl] -ammonium, hexadecyl-dimethyl- [3- ( tris-alkyloxysilyl) -propyl] -ammonium, hexadecyl-dimethyl- [2- (tris-alkyloxysilyl) -ethyl] -ammonium, tetradecyl-dimethyl- [3- (tris-alkyloxysilyl) -propyl] -ammonium, tetradecyl-dimethyl- [2- (trisalkyloxysilyl) ethyl] ammonium, dodecyldimethyl [3- (trisalkyloxysilyl) -propyl] -ammonium, dodecyldimethyl- [2- (trisalkyloxysilyl) -ethyl] -ammonium, decyldimethyl- [3- (tris-alkyloxysilyl) -propyl] -ammonium and decyl-dimethyl- [2- (tris-alkyloxysilyl) -ethyl] -ammonium, where the counterions for the ammonium groups are in each case chloride, bromide, iodide, tosylate, sulfate, hydrogensulfate, Phosphate, hydrogen phosphate, dihydrogen phosphate, sulfonate and hydrogen sulfonate can serve.

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

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

Preferred compounds (A2) are those 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 (A2) are 3-ammonium-propyl-siloxanes and 2-ammonium-ethylsiloxanes, where the ammonium groups are each as defined above.

Components (B) and (C)

The mixture according to the invention of the compounds (A) comprises at least one reactive diluent (B) and optionally at least one further reactive diluent (C) which is other than (B).

Compounds (B) and (C) are those usually used as reactive diluents. These include z. The reactive diluents as described in PKT Oldring (publisher), 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 are described. Reactive diluents are, for example, esters of (meth) acrylic acid with alcohols which have 1 to 20 C atoms, for example methyl (meth) acrylate, (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. As the polyacrylates or methacrylates of alkoxylated 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 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, polyesterpolyol acrylates, polyetherol acrylates and triacrylate of from one to twenty times alkoxylated, most preferably ethoxylated trimethylolpropane.

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.

The compounds (B) are selected from the group consisting of hydroxyalkyl (meth) acrylates and N-vinyllactams, they are preferably hydroxyalkyl (meth) acrylates. Hydroxyalkyl (meth) acrylates as compounds (B) are, for example, compounds having at least one, preferably exactly one hydroxyl group and at least one, for example 1 to 5, preferably 1 to 4, particularly preferably 1 to 3, very particularly preferably 1 or 2 and in particular exactly one (meth) acrylate group, preferably ω-hydroxyalkyl (meth) acrylates or ((j0-1) -hydroxyalkyl (meth) acrylates, preferably (jo-hydroxyalkyl (meth) acrylates.

Particularly preferred hydroxyalkyl (meth) acrylates (B) are those of the formula H ₂ C =C (R ⁹ ) COO-R ⁸ -OH in which

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. Preference is given to 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, 4-hydroxybutyl acrylate, pentaerythritol triacrylate or trimethylolpropane dimethacrylate, particularly preferably 2-hydroxyethyl acrylate , 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate or 2-hydroxyethyl methacrylate, and most preferably 4-hydroxy-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate or 2-hydroxyethyl methacrylate. In particular, the compound (B) is selected from the group consisting of 4-hydroxy-butyl acrylate and 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 divalent hydrocarbon radical having 2 to 10, preferably 2 to 6, particularly preferably 3 to 5, carbon atoms

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 , very particularly 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 other than the reactive diluent (B). 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.

Compounds (C), as they are usually used as reactive diluents, are known per se to the person skilled in the art. These include z. The reactive diluents as described in PKT Oldring (publisher), 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 are described. 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, pen- taerythritol 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.

Urethane (meth) acrylates 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, for example, be 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, particularly 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, more preferably 2 to 4 per 1000 g of epoxy (meth) acrylate or vinyl ether epoxide (determined by gel permeation chromatography with 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 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 are obtainable 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 transesterification with (meth) acrylic esters, as it 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 e.g. 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, for example, 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 (meth) acrylates of one to twenty times and particularly preferably three to ten times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated neopentyl glycol, trimethylolpropane, Trimethylolethane or pentaerythritol.

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, polyesterpolyol acrylates, polyetherol acrylates and acrylate of one to twenty times alkoxylated, most preferably ethoxylated trimethylolpropane. 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 coating compositions 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-yellowing or slightly yellowing photoinitiators of the phenylglyoxalic acid 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-trimethylbenzophenone and 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-benzoylcyclohexan-1-ol, 2-hydroxy-2,2- dimethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone and mixtures thereof. The coating compositions 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 radiation-curable compounds (A) and (B) and optionally (C).

The dispersions according to the invention may contain further conventional lacquer additives (E), such as leveling agents, 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 coating compositions according to the invention may contain, based on the sum of the compounds (A) and (B) and optionally (C), from 0 to 10% by weight 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 may be added, e.g. Potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobis / so-butyronitrile, Cyclohexylsulfonylacetylperoxid, di- / sopropylpercarbonat, feri-butyl peroctoate or benzpinacol, and for example such thermally activatable initiators having a half-life at 80 ° C of more than 100 hours, such as di-t-butyl peroxide, cumene hydrochloride, 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.

As chelating agents, e.g. Ethylenediaminetic acid and its salts and ß-diketones be used.

Suitable fillers include silicates, e.g. 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 being available as Tinuvin R brands of Ciba Specialty Chemicals) 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, eg. B. bis (2,2,6,6-tetra-methyl-4-piperidyl) bacinat 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 coating compositions according to the invention are as a rule composed as follows:

(A) 2 to 90, preferably 4 to 80% by weight, particularly preferably 8 to 70% by weight,

(B) 10 to 80, preferably 20 to 70% by weight, particularly preferably 30 to 60% by weight,

(C) 0 to 84% by weight, preferably 0 to 75, particularly preferably 0 to 60 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.

A particularly preferred radiation-curable coating composition contains from 2 to 90% by weight, preferably from 4 to 80% by weight, more preferably from 8 to 70% by weight, of octadecyldimethyl (trimethoxysilyl) propylammonium chloride and from 98 to 10% by weight, preferably from 94 to 20% by weight %, more preferably 92 to 30% by weight of 4-hydroxybutyl acrylate or 2-hydroxyethyl methacrylate, with the proviso that the sum is 100% by weight.

In general, it is sufficient for an antimicrobial effect of the coating compositions according to the invention if, in a coating composition, at least 4% by weight of component (A) and at least 10% by weight of component (B), based on the total amount of components (A) to (E), are present. The antimicrobial effect is evaluated here by the test indicated in the examples with an incubation over 2 hours, the coating compositions according to the invention preferably already exhibit an antimicrobial effect with an incubation over 1.5 hours, more preferably over 1 hour, most preferably over 45 minutes , especially over 30 minutes and even over 10 minutes.

These particularly preferred radiation-curable coating compositions are preferably masterbatches for antimicrobial coating compositions.

The coating compositions 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 grade steel, and plastics, particularly acrylonitrile-butadiene-styrene (ABS) and polycarbonate (PC) plastics.

With particular advantage, the antimicrobial, radiation-curable coating compositions 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 according to the invention being applied to the substrate to be coated in the desired thickness and any volatile constituents of the coating composition present being removed. If desired, this process can be repeated one or more 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 curing is effected 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 for UV curing, which is usually sufficient for crosslinking, is in the range from 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 it is necessary that the cure speed the preparation according to the invention is sufficiently high.

This different chronological course of the curing can be utilized in particular if the coating of the article is followed by a processing step 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 = 11700: 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), major 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. On each test substrate, 15 predefined positions are automatically approached and images are recorded in the three channels phase contrast (P), red (R) and green (G). 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.

Example 1 50 parts of octadecyl-dimethyl- (trimethoxysilyl) propyl ammonium chloride and 50 parts of butanediol monoacrylate with 2 parts of Irgacure ^® 500 was added, applied to slides at a thickness of about 25 μηη dry film thickness, and under a nitrogen atmosphere with ca. 1400 mJ / cm ² cured in an IST exposure system. Subsequently, the slides were thermally cured for 30 min at 100 ° C.

Example 2

There were 25 parts of octadecyl-dimethyl- (trimethoxysilyl) propyl ammonium chloride, 25 parts of butanediol monoacrylate and 50 parts of pentaerythritol triacrylate with 2 parts of Irgacure ^® offset 500 is applied to slide in a layer thickness of about 25 μηη dry film thickness, and under a nitrogen atmosphere about 1400 mJ / cm ² hardened in an IST exposure system. Subsequently, the slides were thermally cured for 120 min at 100 ° C.

Examples 1 and 2 show paints not only with an extremely strong, but also with an extremely rapid antimicrobial effect.

Example 3 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 were applied with a wet film thickness of 400 μηη 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 -Ri R-SLC-So inert) with 2 UV lamps (high pressure mercury lamps type M 400 U2H and type M 400 U2HC) and a Delivery belt speed of 10 m / min under 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. Film from Example 2: 120 min at 100 ° C pendulum hardness 90 sec

The antimicrobial properties do not change significantly.

This shows that a subsequent thermal treatment can improve the mechanical properties of the paints (hardness) without significantly worsening the antimicrobial activity

Example 4 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® Hl 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 cured in an IST exposure system. Subsequently, the slides were thermally cured for 30 min at 100 ° C.

Comparative Example 1 to Example 4:

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.

Example parts% kill after 2

Ammonium Hours (Fluorescence Salt Microscopy)

4 8 100 Vglbsp 1

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

Claims

20

claims

Antimicrobial radiation-curable coating composition containing

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

- (B) at least one reactive diluent selected from the group consisting of

Hydroxyalkyl (meth) acrylates and N-vinyl lactams,

(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.

Coating composition 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.

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

Coating composition according to claim 1, characterized in that the ammonium group carries four hydrocarbon radicals as substituents on the ammonium group.

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

Coating composition 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, pentaerythritol triacrylate, trimethylolpropane dimethacrylate, N-vinylpyrrolidone and N-vinylcaprolactone. 21

Coating composition according to one of the preceding claims, characterized in that it

- At least 4% by weight of component (A) and

contains at least 10% by weight of component (B),

based on the total amount of components (A) to (E).

Coating composition according to one of the preceding claims, characterized in that it is composed as follows:

(A) 2 to 90% by weight

(B) 10 to 80% by weight

(C) 0 to 84% 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.

Use of coating composition 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.

10. Use of coating material according to one of claims 1 to 8 for coating medical devices and objects.

Process for the antimicrobial treatment of substrates, characterized in that a coating composition according to one of Claims 1 to 8 is applied to the substrate, optionally dried and then cured with high-energy radiation.

12. Radiation curable coating compositions containing,

From 2 to 90% by weight, preferably from 4 to 80% by weight, particularly preferably from 8 to 70% by weight, of octadecyldimethyl (trimethoxysilyl) propylammonium chloride and

From 98 to 10% by weight, preferably from 94 to 20% by weight, particularly preferably from 92 to 30% by weight, of 4-hydroxybutyl acrylate or 2-hydroxyethyl methacrylate,

with the proviso that the sum is 100% by weight.

13. Use of radiation-curable coating composition according to claim 12 as master batches for antimicrobial coating compositions.