WO2013110566A1 - Matière de revêtement antimicrobienne durcissable par rayonnement - Google Patents

Matière de revêtement antimicrobienne durcissable par rayonnement Download PDF

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WO2013110566A1
WO2013110566A1 PCT/EP2013/051030 EP2013051030W WO2013110566A1 WO 2013110566 A1 WO2013110566 A1 WO 2013110566A1 EP 2013051030 W EP2013051030 W EP 2013051030W WO 2013110566 A1 WO2013110566 A1 WO 2013110566A1
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weight
meth
coating composition
composition according
carbon atoms
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PCT/EP2013/051030
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German (de)
English (en)
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Reinhold Schwalm
Rupert Konradi
Herbert Platsch
Christina Haaf
Catharina Hippius
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Basf Se
Basf Schweiz Ag
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Publication of WO2013110566A1 publication Critical patent/WO2013110566A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

Definitions

  • 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.
  • 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.
  • 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 spacer comprises at least one carbon atom, preferably at least two carbon atoms.
  • 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.
  • 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.
  • the quaternary ammonium group has the following formula (I)
  • R 4 is a 1 to 10, preferably 2 to 6, particularly preferably 2 to 4 carbon atoms containing divalent hydrocarbon radical
  • 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.
  • aryl groups having 6 to 14 carbon atoms are phenyl, ⁇ -naphthyl and ⁇ -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.
  • 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.
  • 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)
  • 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] am
  • 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.
  • Preferred compounds (A2) are those of the formula (IV)
  • R 1 to R 4 have the above meanings and
  • 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,
  • hexanediol diacrylate hexanediol dimethacrylate, octanediol diacrylate, octanediol dimethacrylate, nonanedioldiacrylate, nonanediol dimethacrylate, decanediol diacrylate, decanediol dimethacrylate, pentaerythritol diacrylate, dipentaerythritol tetraacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, etc.
  • esters of alkoxylated polyols with ⁇ , ⁇ -ethylenically unsaturated are also preferred Mono- and / or dicarboxylic acids such.
  • polyacrylates or methacrylates of alkoxylated trimethylolpropane, glycerol or pentaerythritol are also suitable.
  • 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.
  • 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 ⁇ -hydroxyalkyl (meth) acrylates or ((j0-1) -hydroxyalkyl (meth) acrylates, preferably (jo-hydroxyalkyl (meth) acrylates.
  • 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.
  • 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.
  • R 10 is a divalent hydrocarbon radical having 2 to 10, preferably 2 to 6, particularly preferably 3 to 5, carbon atoms
  • N-vinyllactams as compounds (B) are N-vinylpyrrolidone or N-vinylcaprolactam.
  • 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.
  • 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.
  • 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.
  • 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 pentaeryth
  • esters of alicyclic diols such as cyclohexanediol di (meth) acrylate and bis (hydroxymethyl-ethyl) cyclohexane-di (meth) acrylate.
  • 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:
  • 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).
  • Particularly preferred urethane (meth) acrylates have an average functionality of 1.5 to 4.5.
  • 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.
  • 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.
  • 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.
  • 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
  • polyester (meth) acrylates are at least partially or preferably completely
  • 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.
  • (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.
  • 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
  • the carbonate (meth) acrylates are preferably aliphatic carbonates (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.
  • 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.
  • 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 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.
  • E lacquer additives
  • 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.
  • 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.
  • 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.
  • thermally activatable initiators having a half-life at 80 ° C of more than 100 hours, such as di-t-butyl peroxide, cumene hydrochloride, dicumyl per
  • 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.
  • (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,
  • 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.
  • 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.
  • ABS acrylonitrile-butadiene-styrene
  • PC polycarbonate
  • 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.
  • NIR radiation here electromagnetic radiation in the wavelength range of 760 nm to 2.5 ⁇ , preferably from 900 to 1500 nm is designated.
  • 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.
  • 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
  • P. aeruginosa ATCC 15442 (incubation at 30 ° C): preculture 100% DSM 546 medium (LC medium), major culture 10% DSM 546 medium
  • 500 ⁇ _ the main culture bacteria are according to the manufacturer's recommendation with 1, 5 to 9 ⁇ _ SY fluorescent dye and 1, 5 ⁇ _ propidium iodide fluorescent dye (film Tracer TM LIVE / DEAD ® Viability Kit biofilm, Fa. Invitrogen) stained.
  • 10 ⁇ _ of this bacterial suspension are placed on the surface to be examined and covered with a coverslip. In this case, an approximately 30 ⁇ 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).
  • 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.
  • P phase contrast
  • R red
  • G green
  • 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 ⁇ 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.
  • Examples 1 and 2 show paints not only with an extremely strong, but also with an extremely rapid antimicrobial effect.
  • the antimicrobial properties do not change significantly.
  • 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 ⁇ 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 4 shows that methacrylic acid instead of the reactive diluent (B) shows no effect according to the invention.

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Abstract

La présente invention concerne une matière de revêtement antimicrobienne durcissable par rayonnement, son procédé de préparation et son utilisation.
PCT/EP2013/051030 2012-01-27 2013-01-21 Matière de revêtement antimicrobienne durcissable par rayonnement WO2013110566A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021234162A2 (fr) 2020-05-22 2021-11-25 Lithcote-Europe Revêtement nano-céramique, hybride, transparent et biocide pour support solide et support solide comportant un tel revêtement et son procédé d'obtention

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021234162A2 (fr) 2020-05-22 2021-11-25 Lithcote-Europe Revêtement nano-céramique, hybride, transparent et biocide pour support solide et support solide comportant un tel revêtement et son procédé d'obtention

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