WO2008058885A2 - Matières de revêtement durcissables par rayonnement - Google Patents

Matières de revêtement durcissables par rayonnement Download PDF

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WO2008058885A2
WO2008058885A2 PCT/EP2007/062049 EP2007062049W WO2008058885A2 WO 2008058885 A2 WO2008058885 A2 WO 2008058885A2 EP 2007062049 W EP2007062049 W EP 2007062049W WO 2008058885 A2 WO2008058885 A2 WO 2008058885A2
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group
ions
butyl
alkyl
optionally substituted
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PCT/EP2007/062049
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WO2008058885A3 (fr
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Sylke Haremza
Michael BÜSCHEL
Gerhard Wagenblast
Erich Beck
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents

Definitions

  • the present invention relates to radiation-curable coating compositions containing NIR photoinitiators, new formulations of NIR photoinitiators and their use.
  • EP 408 322 describes one-component photoinitiators in the form of the salts of cyanine dye and certain borane ions.
  • these photoinitiator systems are solids which, as such, entail all the disadvantages of solids handling.
  • Most NIR photoinitiator systems known in the literature must be dissolved in solvent for liquid meterability, which disadvantageously introduces volatile organic compounds (VOCs) into the coating composition.
  • VOCs volatile organic compounds
  • WO 2006/058731 describes NIR photoinitiator systems which have good solubility.
  • the co-initiators listed there in the examples are solids, which accordingly have to be metered as solids.
  • EP 900800 A2 (US 6562543, US 6218076) describes a large number of heterocycles, amines and thiols as stabilizer compounds for the boranate salt, which in turn may have ammonium, quinolinium, pyridinium, phosphonium and other cations as the counterion.
  • the stabilizer component is used in each case as the free base and not as a counterion to the boronate.
  • the boronate-cation complexes formed in the examples must each be brought into solution with a solvent, and consequently they are not liquids.
  • cetylpyridinium and trimethylcetylammonium as counterions to boronate co-initiators.
  • cetylpyridnium n-butyl triphenyl boranate has a melting point of 38 0 C (see comparative examples).
  • US 6846605 describes boronate cation complexes as co-initiators which have a melting point below 100 0 C. The adjustment of the melting point takes place here via the choice of the substituents in the boranate, whereas cations which are conventional as counterions, such as metal ions or tetraalkylammonium ions.
  • benzyltrimethylammonium n-butyl triphenyl boranate has a melting point of 149 0 C (see comparative examples).
  • US 5854298 uses butyrylcholine as a cation for the boranate in the examples. Since the co-initiator used is a solid, the resulting mixture must be mixed consuming.
  • JP 9-197841 describes liquid-crystalline mixtures containing boron ions with ammonium ions as counterion
  • This invention describes two-component NIR photoinitiator systems which comprise at least one sensitizer dye, also called sensitizer, and at least one free-radical initiator, also called co-initiator.
  • Dyes in particular cyanine, xanthylium or thiazine dyes, are frequently used as the sensitizing dye in the prior art, and the co-initiators are, for example, boranate salts, sulfonium salts, iodonium salts, sulfones, peroxides, pyridine-N-oxides or halomethyltriazines.
  • Cyanine dyes consist of a cyanine cation and a corresponding anion. This may be a separately present anion or else an inner anion, ie the anionic group is chemically linked to the cyanine cation.
  • Cyanine dyes with anions which have long-chain alkyl or alkyl-substituted aryl groups are known from WO 2006/058731. Cyanine dyes are commercially available.
  • Cyanine dyes are often used as alkyl and aryl sulfonates, sulfates, chlorides or the like, as known, for example, from US 6 014 930 or EP-A 342 576.
  • DE-A 197 30 498 and DE-A 196 48 256 disclose compositions which are prepared from the separate salts of a cationic dye and boranate salts and can also be used in mixtures with UV photoinitiators.
  • cyanine dyes as NIR absorbers for laser radiation which have a minimum solubility of 0.1% by weight in printing inks and which can have as counterions borates which carry substituents bound to four oxygen atoms at the central boron atom.
  • borates are photochemically inactive and can not function as photoinitiators.
  • the object of the present invention was to provide NIR photoinitiator systems which, on the one hand, have good solubility and, on the other hand, have good photoactivability by NIR radiation and, moreover, should be easy to incorporate into coating compositions.
  • n 1 or 2
  • U, V, W, X, Y independently represent CH or N.
  • R 1 to R 9 denote the following:
  • R 1 and R 2 independently of one another represent a linear or branched, optionally further substituted alkyl or aralkyl radical having 1 to 20 C atoms,
  • R 3 and R 4 independently of one another are H, CF 3 or CN,
  • R 5 and R 6 independently of one another are one or more identical or different substituents selected from the group consisting of -H, -F, -Cl, -Br, -I, -NO 2 , -CN, -CF 3 , -SO 2 CF. 3 , -R 1 , -OR 1 , aryl or -O-aryl,
  • R 7 is -H, -Cl, -Br, -I, -phenyl, -O-phenyl, -S-phenyl, -N (phenyl) 2 , -pyridyl, a barbituric acid or a dimedone radical, the phenyl radicals also being can be further substituted,
  • An m - is a borate anion of the general formulas (IX) or (X)
  • R 10 is as defined above and R 12 is at least one substituent selected from the group of H or linear, cyclic or branched alkyl groups having 1 to 20 C atoms, and
  • radicals R 10 , R 11 and R 12 also non-adjacent C atoms may optionally be substituted by O atoms and / or the radicals R 10 , R 11 and R 12 may be completely or partially fluorinated, with the proviso that the non-polar character of the groups is not significantly affected thereby and
  • z 1 , z 2 , z 3 and z 4 are each independently 0 or 1,
  • Y 1 , Y 2 , Y 3 and Y 4 are each independently O, S or NR 17 ,
  • R 13 , R 14 , R 15 and R 16 each independently of one another are C 1 -C -alkyl, C 2 -C -alkyl which is optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups Ci2-aryl, C5 - Ci2-cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle, wherein said
  • Radicals may each be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, and
  • R 17 is hydrogen, C i - C 8 alkyl or C 6 -alkyl - Ci 2 -aryl
  • radicals R 13 to R 16 are a C 1 -C 6 -alkyl radical and at least one of the radicals R 13 to R 16 is a C 6 -C 12 -aryl radical, where the radicals mentioned are in each case represented by aryl, alkyl, aryloxy, Alkyloxy, heteroatoms and / or heterocycles can be substituted
  • cation is selected from the group consisting of pyridazinium ions, pyrimidinium ions, pyrazinium ions, imidazolium ions, 1 H-pyrazolium ions, 3H-pyrazolium ions, 4H-pyrazolium ions, 1-pyrazolinium ions, 2-pyrazolinium ions, 3-pyrazolinium ions, imidazolinium ions, thiazolium ions, 1, 2,4-triazolium ions, 1, 2,3-triazolium ions, pyrrolidinium ions, diammonium ions or alkylene oxide-bridged diammonium ions.
  • the melting point is preferably measured by means of DSC (Differential Scanning Calorimetry), particularly preferably with a device DSC823e from Mettler-Toledo at a heating rate of 2.00 ° C./min.
  • Ci-cis-alkyl for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1
  • At least one carbon atom preferably at least two, is usually present between two heteroatoms.
  • Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino groups.
  • C 3 -C 12 aryl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example phenyl, ToIyI, XyIyI, ⁇ -naphthyl, ⁇ -naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, Methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl,
  • aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Cs - Ci2-cycloalkyl for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, Dimethoxycyclohexyl, Diethoxycyclohexyl, Butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as Norbornyl or norbornenyl and
  • a five- to six-membered heterocycle having oxygen, nitrogen and / or sulfur atoms for example furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, Dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • Y 1, Y 2, Y 3 and Y 4 are preferably each independently oxygen or NR 17, and most preferably oxygen.
  • R 17 is preferably hydrogen or C 1 -C 4 -alkyl.
  • C 1 -to-C 4 -alkyl in this application is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, preferably methyl, ethyl or n-butyl, more preferably methyl or ethyl, and very particularly preferred for methyl.
  • R 13 , R 14 , R 15 and R 16 are each preferably, independently of one another, C 1 -C 6 -alkyl, C 6 -C 12 -aryl or C 5 -C 12 -cycloalkyl, preferably C 1 -Cis-alkyl and C 6 -C 12 -aryl, very particularly preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, Dodecyl, tetradecyl, heptadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3,3-tetramethylbutyl, benzyl,
  • R 13 to R 16 of at least one C 1 -C 6 -alkyl and at least one C 6 -C 12 -aryl preferably at least one C 1 -C -alkyl and at least one C 6 -C 12 -aryl and the other two are likewise selected from of the group comprising C 1 -C 6 -alkyl and C 6 -C 12 -aryl, particularly preferred are at least one C 1 -C 6 -alkyl and at least two C 6 -C 12 -aryl and very particularly preferably one C 1 -Cis -alkyl and three C 6 -C 12 -aryl aryl.
  • the amount of sensitizing dye contained in the coating composition according to the invention is selected by the person skilled in the art so that sufficient photocuring of the coating composition is achieved. As a rule, an amount of less than 5% by weight is sufficient.
  • An amount of from 0.05 to 4% by weight, based on the sum of all components of the coating composition, has preferably proven itself, preferably from 0.1 to 3% by weight, more preferably from 0.2 to 2.5% by weight and very particularly preferably from 0 , 3 to 2.0% by weight. It must be ensured according to the invention that added sensitizing dye is completely dissolved in the coating composition.
  • the solubility of the sensitizing dye in the coating composition is preferably at least 0.2% by weight, more preferably at least 0.5% by weight, very preferably at least 1.0% by weight and for example at least 2% by weight.
  • the sensitizing dye is an ionic absorber composed of a cyanine cation Cya + and a corresponding anion 1 / m An m , where m can in particular have the values 1 or 2.
  • the cyanine cation according to the invention has a general formula selected from the following formulas (I) to (IV):
  • R 1 and R 2 independently of one another represent a linear or branched alkyl or aralkyl radical having 1 to 20 C atoms. Examples include methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, t-butyl, 1-pentyl, 1-hexyl, 2-ethyl-1 hexyl, 1-octyl, 1-decyl or 1-dodecyl groups. In particular, they are linear alkyl groups.
  • Preferred radicals are methyl, ethyl, 1-butyl or 1-dodecyl groups.
  • Aralkyl groups are, in a manner known in principle, alkyl groups substituted with aryl groups. Examples include a benzyl or phenylethyl group.
  • R 1 and R 2 may be the same or different from each other.
  • R 1 and R 2 are preferably identical radicals.
  • R 1 and R 2 may optionally be further substituted. Particularly noteworthy here are functional groups such as amino or hydroxy groups. If present, these may be, in particular, functional groups terminally attached to alkyl groups.
  • R 3 and R 4 are independently -H, CF 3 or -CN. Preferably, R 3 and R 4 are the same group.
  • R 5 and R 6 are various or preferably identical radicals selected from the group of -H, -F, -Cl, -Br, -I, -NO 2, -CN, -CF 3 or -SO 2 CF 3 , R 5 and R 6 may also be a radical -R 1 or -OR 1 , where R 1 is each as defined above. Furthermore, it may be aryl or -O-aryl radicals, wherein aryl is preferably a phenyl radical.
  • R 5 and R 6 are preferably -H, -Cl, -Br or -I or an alkyl radical.
  • the terminal rings may each also have a plurality of identical or different substituents R 5 or R 6 at different positions of the ring. Preferably, no more than two substituents are present on each ring, more preferably only one each.
  • R 7 may be -H, -Cl, -Br, -I, -phenyl, -O-phenyl, -S-phenyl, -N (phenyl) 2 , -pyridyl, a barbituric acid or a dimedone radical, where the phenyl radicals can also be further substituted.
  • Other substituents may be, for example, straight-chain or branched alkyl radicals, for example methyl or ethyl radicals, or else -F, -Cl, -Br, -I, -NO 2, -CN or -CF 3.
  • An m - may for example be selected from the group consisting of halide, pseudohalide, sulfate and sulfonate.
  • Halide is, for example, fluoride, chloride, bromide and iodide.
  • Pseudohalide for example CN, OCN or SCN.
  • Sulfate is, for example, R 36 -O-SO 3 " , in which R 36 is a linear or branched alkyl or aralkyl radical having 1 to 20 C atoms or C 6 -C 12 -aryl or C 1 -C 12 -cycloalkyl Examples are methylsulfate, ethylsulfate and n -Butylsulfat.
  • Sulfonate is, for example, R 37 -SC "3" in which R 37 is a linear or branched alkyl or aralkyl radical having 1 to 20 C atoms, or C 6 -C 12 -aryl or C 12 -C 12 -cycloalkyl, which may optionally be substituted by halogen can.
  • R 37 is a linear or branched alkyl or aralkyl radical having 1 to 20 C atoms, or C 6 -C 12 -aryl or C 12 -C 12 -cycloalkyl, which may optionally be substituted by halogen can.
  • examples thereof are benzenesulfonate, p-tolylsulfonate, cyclododecylsulfonate, camphorsulfonate, methylsulfonate or trifluoromethylsulfonate.
  • the counterion An m " to the cyanine cation may further have the general formula [AR 1o k] m" . It comprises at least one polar, ionic head group A and k nonpolar groups R 10 , where k is a number of 1, 2 or 3 and m is 1 or 2.
  • the anion preferably has only one group R 10 . Furthermore, it is preferably monovalent anion. If several nonpolar groups R 10 are present in the anion, they may be different or preferably similar. Of course, it may also be a mixture of several different anions.
  • the groups R 10 may be linear, branched or cyclic alkyl groups having 6 to 30 carbon atoms.
  • the alkyl groups R 10 preferably have 6 to 12 C atoms.
  • suitable groups include 1-hexyl, cyclohexyl, 2-ethyl-1-hexyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl or 1-tetradecyl groups. They are preferably linear alkyl groups.
  • alkylaryl groups of the general formula -aryl-R 11 , where R 11 is a linear or branched alkyl group having 3 to 30 C atoms.
  • suitable groups include 1-propyl, 2-propyl, 1-butyl, 2-butyl, tert-butyl, 1-pentyl, 1-hexyl, cyclohexyl, 2-ethyl-1-hexyl , 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl or 1-tetradecyl groups.
  • the alkyl groups R 11 preferably have 6 to 12 C atoms. Particularly preferred are linear alkyl groups.
  • the aryl moiety is a group formed by formal abstraction of the corresponding number of hydrogen atoms from an aromatic hydrocarbon, preferably benzene or naphthalene.
  • the aryl unit is in particular a phenylene group, preferably a 1,4-phenylene group.
  • suitable alkylaryl groups include - (C 6 H 4) -C 3 H7, - (C 6 H 4) -C6Hi3, or - (C 6 H 4) -Ci2H 2. 5
  • the polar ionic head group A is, in particular, the anion of a monovalent or divalent acid radical. It may be any inorganic or organic acid group. It is preferably a carboxyl group or acidic groups containing S, P and / or B groups. For example, it may be an acid group selected from the group consisting of -SO 3 ", -OSO3", -COO ", -PO 3 2 -, -OPO 3 2 - or (-O) PO 2" act.
  • alkylsulfonates having alkyl radicals in particular linear alkyl radicals having from 6 to 12 carbon atoms, such as, for example, n-octylsulfonate, n-decylsulfonate or n-dodecylsulfonate, and also 4-alkylbenzenesulfonates having alkyl radicals of from 6 to 12 carbon atoms
  • 4-hexylbenzenesulfonate, 4-octyl benzenesulfonate, 4-decylbenzenesulfonate or 4-dodecylbenzenesulfonate may also be technical products which have a distribution of different alkyl radicals of different lengths.
  • An m - for the cyanine cation may also be a borate anion of the general formulas (IX) or (X)
  • R 10 is a radical as defined above. There may be one or two identical or different substituents on each of the chelating ligands. Preferably, in each case one substituent is present.
  • R 12 is in each case one or more identical or different substituents selected from the group of H or linear, cyclic or branched alkyl groups having 1 to 20 C atoms, preferably a radical having 2 to 12 C atoms. Preferably, only one alkyl group is present as a substituent.
  • Such borate anions are obtainable, for example, from boric acid and the corresponding dialcohol.
  • non-adjacent carbon atoms may optionally be substituted by oxygen atoms and / or the radicals R 10 , R 11 and R 12 may be completely or partially fluorinated, provided that Non-polar character of the groups is not significantly changed. In a preferred embodiment, the residues are not fluorinated.
  • the preparation of the sensitizing dyes according to the invention can be carried out by various methods. They can be prepared, for example, by means of a two-stage process in which, in a first step, the cyanine cations are synthesized with customary anions such as iodide, tetrafluoroborate, perchlorate or paratoluenesulfonate. Manufacturing instructions are known in the art. As an example reference may be made to DE-A 37 21 850, EP-A 627 660 and the literature cited therein. Cyanine-based sensitizing dyes are also commercially available.
  • the customary anions are then exchanged for the anions An m "according to the invention by means of a suitable process.
  • the absorber must not be soluble therein.
  • Particularly suitable are volatile organic solvents with a certain polarity. For example, it may be dichloromethane.
  • the organic solution or suspension is then extracted with water until the original anion is completely removed from the organic solution.
  • the sensitizer dye according to the invention can be obtained by removing the solvent from the solution.
  • the preparation can also be carried out using acidic ion exchange resins.
  • the ion exchange can also be carried out in accordance with the method disclosed by WO 03/76518.
  • the mixtures according to the invention also contain a component (B) of an anionic boron compound of the formula (XI).
  • anionic boron compounds have as counterion an x-fold positively charged cation Kat x + , which is selected so that according to the invention the melting point of the mixture Kat x + boranate not more than 120 0 C, preferably not more than 100 0 C, more preferably not more than 80 0 C, most preferably not more than 60 0 C, in particular not more than 35 0 C and especially not more than 20 0 C.
  • the melting points of these compounds are determined on mixtures having a purity of at least 90%, preferably at least 95%, more preferably at least 97% and most preferably at least 98%. Any by-products and solvents should be removed as far as possible.
  • the cations are preferably Kat x + selected from the compounds of the formulas (XIIb) to (XIIw),
  • R 48 is a C 6 -C 12 -arylene, C 3 -C 12 -cycloalkylene, C 1 -C 20 -alkylene or by one or more O, S or N atoms and / or by one or more - (CO) -, - 0 (CO) O-, - (NH) (CO) O-, -O (CO) (NH) -, -O (CO) - or - (CO) O- groups interrupted C1-C20 alkylene.
  • R 49 hydrogen or methyl
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 and R 47 are each independently hydrogen, Ci - Ci8-alkyl, optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C 2 - Cis-alkyl, C ⁇ - Ci 2 -aryl, Cs - Ci 2 -cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle or two of them together one form an unsaturated, saturated or aromatic ring optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, said radicals being in each case denoted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, Heteroatoms and / or heterocycles can be substituted.
  • R 47 can furthermore Ci - Cis-alkyloyl (alkylcarbonyl) Ci - Ci ⁇ - alkyloxycarbonyl, Cs - Ci 2 cycloalkylcarbonyl or C ⁇ - mean Ci 2 -Aryloyl (arylcarbonyl), where the radicals mentioned in each case by functional groups, aryl, alkyl Aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles may be substituted.
  • C 1 -C -alkyl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, Hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3,3-tetramethylbutyl, Benzyl, 1-phenylethyl, 2-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1-
  • radicals may together be 1, 3-propylene, 1, 4-butylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propylene, 2-oxa 1, 3-propylene, 1-oxa-1, 3-propenylene, 1-aza-1, 3-propenylene, 1-Ci-C4-alkyl-1-aza-1, 3-propenylene, 1, 4-buta- 1, 3-dienylene, 1-aza-1, 4-buta-1, 3-dienylene or 2-aza-1, 4-buta-1, 3-dienylene.
  • the number of oxygen and / or sulfur atoms and / or imino groups is not limited. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3.
  • Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
  • aryl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ⁇ - Ci2-aryl for example phenyl, ToIyI, XyIyI, ⁇ -naphthyl, ß-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trich lorphenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chlorona
  • C 5 -C 12 -cycloalkyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, Me - Thoxycyclohexyl, dimethoxycyclohexyl, Diethoxycyclohexyl, Butylthiocyclohexyl, chloro-cyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as Norbornyl or norbornenyl,
  • a five- to six-membered heterocycle having oxygen, nitrogen and / or sulfur atoms for example furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, Difluorpyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl and
  • Ci to C4-alkyl for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • C 1 -C 6 -alkyloyl may be, for example, acetyl, propionyl, n-butyloyl, sec-butyloyl, tert-butyloyl, 2-ethylhexylcarbonyl, decanoyl, dodecanoyl, chloroacetyl, trichloroacetyl or trifluoroacetyl.
  • C 1 -C 18 -alkyloxycarbonyl may be, for example, methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, sec-butyl oxycarbonyl, tert-butyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl or benzyloxycarbonyl.
  • C 5 -C 12 -cycloalkylcarbonyl may be, for example, cyclopentylcarbonyl, cyclohexylcarbonyl or cyclododecylcarbonyl.
  • C ⁇ -C 12 aryloyl may be, for example, benzoyl, toluyl, xyloyl, ⁇ -naphthoyl, ⁇ -naphthoyl, chlorobenzoyl, dichlorobenzoyl, trichlorobenzoyl or trimethylbenzoyl.
  • R 41 , R 42 , R 43 , R 44 , R 45 and R 46 are independently hydrogen, methyl, ethyl, n-butyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- ( Ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, dimethylamino, diethylamino and chloro.
  • R 47 is preferably hydrogen, methyl, ethyl, n-butyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, acetyl, Propionyl, t-butyryl, methoxycarbonyl, ethoxycarbonyl or n-butoxycarbonyl.
  • Particularly preferred pyridazinium ions are those in which one of the radicals R 41 to R 44 is methyl or ethyl, R 47 is hydrogen, acetyl, methyl, ethyl or n-butyl and all other hydrogen or R 47 is hydrogen, acetyl, methyl, ethyl or n-butyl, and all others are hydrogen.
  • Particularly preferred pyrimidinium ions are those in which R 42 to R 44 is hydrogen or methyl, R 47 is hydrogen, acetyl, methyl, ethyl or n-butyl and R 41 is hydrogen, methyl or ethyl, or R 42 and R 44 is methyl , R 43 is hydrogen and R 41 is hydrogen, methyl or ethyl and R 47 is hydrogen, acetyl, methyl, ethyl or n-butyl.
  • Particularly preferred pyrazinium ions are those in which R 41 to R 44 are all methyl and
  • R 47 is hydrogen, acetyl, methyl, ethyl or n-butyl or R 47 is hydrogen, acetyl, methyl, ethyl or n-butyl and all others are hydrogen.
  • Particularly preferred imidazolium ions are those in which independently of one another
  • R 41 is selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, 2-hydroxyethyl and 2-cyanoethyl
  • R 47 is hydrogen, acetyl, methyl, ethyl or n-butyl and
  • R 42 to R 44 independently of one another denote hydrogen, methyl or ethyl.
  • Particularly preferred 1 H-pyrazolium ions (XIIf) are those in which independently of one another
  • R 41 is selected from hydrogen, methyl or ethyl
  • R 42 , R 43 and R 44 are hydrogen and methyl
  • R 47 is hydrogen, acetyl, methyl, ethyl and n-butyl.
  • Particularly preferred 3H-pyrazolium ions are those in which independently of one another
  • R 41 is hydrogen, methyl and ethyl
  • R 42 , R 43 and R 44 are hydrogen, and methyl and
  • R 47 are selected from hydrogen, acetyl, methyl, ethyl and n-butyl.
  • Particularly preferred 4H-pyrazolium ions are those in which independently of one another R 41 to R 44 are hydrogen and methyl and
  • R 47 are selected from hydrogen, acetyl, methyl, ethyl and n-butyl.
  • Particularly preferred 1-pyrazolinium ions are those in which independently of one another R 41 to R 46 are hydrogen and methyl and
  • R 47 are selected from hydrogen, acetyl, methyl, ethyl and n-butyl.
  • 2-pyrazolinium ions (XIIj) are those in which, independently of one another, R 41 is hydrogen, methyl, ethyl and phenyl,
  • R 47 is selected from hydrogen, acetyl, methyl, ethyl and n-butyl and R 42 to R 46 are selected from hydrogen and methyl.
  • Particularly preferred 3-pyrazolinium ions are those in which independently of one another
  • R 41 or R 42 are selected from hydrogen, methyl, ethyl and phenyl
  • R 47 is selected from hydrogen
  • R 43 to R 46 are selected from hydrogen and methyl.
  • imidazolinium ions (XIII) are those in which independently of one another
  • R 41 or R 42 is hydrogen, methyl, ethyl, n-butyl and phenyl,
  • R 47 is hydrogen, acetyl, methyl, ethyl and n-butyl and
  • R 43 or R 44 are selected from hydrogen, methyl and ethyl and R 45 or R 46 are selected from hydrogen and methyl.
  • Particularly preferred imidazolinium ions (XIIm) are those in which independently of one another
  • R 41 or R 42 are selected from hydrogen, methyl and ethyl
  • R 47 is selected from hydrogen, acetyl, methyl, ethyl and n-butyl
  • R 43 to R 46 are selected from hydrogen and methyl.
  • imidazolinium ions are those in which independently of one another
  • R 41 , R 42 or R 43 are hydrogen, methyl and ethyl
  • R 47 is hydrogen, acetyl, methyl, ethyl and n-butyl and
  • R 44 to R 46 are selected from hydrogen and methyl.
  • Particularly preferred thiazolium ions (XIIo) or oxazolium ions (XIIp) are those in which, independently of one another, R 41 is hydrogen, methyl, ethyl and phenyl,
  • R 47 is selected from hydrogen, acetyl, methyl, ethyl and n-butyl and R 42 or R 43 are selected from hydrogen and methyl.
  • 1,2,4-triazolium ions (XIIq) and (XIIr) are those in which independently of one another
  • R 41 or R 42 are selected from hydrogen, methyl, ethyl and phenyl
  • R 47 is selected from hydrogen, acetyl, methyl, ethyl and n-butyl
  • R 43 is selected from hydrogen, methyl and phenyl.
  • 1,2,3-triazolium ions are those in which independently of one another
  • R 41 is hydrogen, methyl and ethyl
  • R 47 is hydrogen, acetyl, methyl, ethyl and n-butyl and
  • R 42 or R 43 are selected from hydrogen and methyl, or R 42 and R 43 are 1, 4-buta-1,3-dienylene and all others are hydrogen.
  • pyrrolidinium ions are those in which independently of one another
  • R 41 and R 47 are selected from hydrogen, acetyl, methyl, ethyl and n-butyl and R 42 , R 43 , R 44 and R 45 are hydrogen.
  • the radicals R 41 to R 46 are independently selected from the group consisting of methyl, ethyl, n-butyl, benzyl, 2-hydroxyethyl and 2-hydroxypropyl, more preferably from methyl and benzyl ,
  • R 48 is preferably selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1, 8-octylene, 1, 10-decylene and 1, 12-dodecylene.
  • Preferred cations are those which have at least one permanent cationic center, ie in the formulas (XII b to u) R 47 ⁇ hydrogen.
  • pyrrolidinium ions (XIIu) are less preferred.
  • the imidazolium ions are preferred.
  • co-initiator mixtures consisting of at least one component (B) of the formula (XI), with a counterion V x Kat x + , which have a melting point as above.
  • Preferred co-initiator mixtures according to the invention are those which have a solubility at 25 ° C. in ethyl acetate of at least 10% by weight, preferably at least 15% by weight, very particularly preferably at least 20% by weight, in particular at least 35% by weight and at least 50% by weight.
  • compositions according to the invention contain at least one component (A) of the formula V m An m - Cya + , as indicated above, and at least one component (B), preferably of the formula (XI), with a counterion V x Kat x + .
  • the mixtures according to the invention may contain, as component (B), in addition to the anionic boron compounds of the formula (XI) with their counterion V x Kat x +, also sulphonium salts, iodonium salts, sulphones, peroxides, pyridine-N-oxides or halomethyltriazines.
  • component (B) in addition to the anionic boron compounds of the formula (XI) with their counterion V x Kat x +, also sulphonium salts, iodonium salts, sulphones, peroxides, pyridine-N-oxides or halomethyltriazines.
  • Suitable sulfonium salts are described, for example, in DE-A1 197 30 498, there in particular on page 3, lines 28-39, which are hereby expressly the subject of the present disclosure by reference.
  • R 18 and R 19 each represent an optionally substituted aryl group
  • R 20 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alicyclic group, an optionally substituted aryl group or an optionally substituted aralkyl group, and
  • AnA- represents an anion.
  • triphenylsulfonium diphenylanisylsulfonium, diphenyl (4-tolyl) sulfonium, diphenyl (4-fluorophenyl) sulfonium, diphenyl [4- (phenylthio) phenyl] sulfonium, diphenylbenzylsulfonium, diphenyl (4-chlorobenzyl) -sulfonium, diphenyl- (4-bromobenzyl) sulfonium, diphenyl- (4-cyano-benzyl) -sulfonium, di- (4-tert-butylphenyl) -benzylsulfonium, dianisyl (4-bromophenylsulfonium, diphenylphenacylsulfonium, diphenyl- (4-chlorophenacyl) sulfonium , Diphenyl- (4-cyanoph
  • Preferred anions AnA- are BF 4 -, PF ⁇ “ , AsF ⁇ “ , SbF ⁇ “ , CIO 4 " , Ch, Br, tetraphenylborate, tetrakis (pentafluorophenyl) borate, the benzenesulfonate anion, the p-toluenesulfonate anion and the trifluoromethanesulfonate anion.
  • Suitable iodonium salts are described, for example, in DE-A1 197 30 498, there in particular on page 3, lines 40-43, which is hereby expressly the subject of the present disclosure by reference.
  • R 21 and R 22 are optionally substituted aryl groups and AnB- is an anion.
  • diphenyliodonium anisylphenyliodonium, di (4-tert-butylphenyl) iodonium, di (4-chlorophenyl) iodonium, di-tolyliodonium and di (3-nitrophenyl) iodonium.
  • Preferred anions AnB- are BF 4 -, PF ⁇ “ , AsF ⁇ “ , SbF ⁇ “ , CIO 4 " , Ch, Br, tetraphenylborate, tetrakis (pentafluorophenyl) borate, the benzenesulfonate anion, the p-toluenesulfonate anion and the trifluoromethanesulfonate anion.
  • Suitable sulfones are described for example in DE-A1 197 30 498, there especially on page 4, lines 1-12, which is hereby expressly subject matter of the present disclosure by reference.
  • R 23 represents an optionally substituted aryl group and the radicals R 24 each represent a halogen atom.
  • Halogen in the context of this document comprises fluorine, chlorine, bromine and iodine, preferably chlorine and bromine and particularly preferably chlorine.
  • trichloromethylphenylsulfone tribromomethylphenylsulfone, trichloromethyl-4-chlorophenylsulfone, tribromomethyl-4-nitrophenylsulfone, 2-trichloromethylbenzothiazolesulfone, 2,4-dichlorophenyltrichloromethylsulfone, 2-methyl-4-chlorophenyltrichloromethylsulfone and 2,4-dichlorophenyltribromomethylsulfone.
  • Suitable peroxides are described for example in DE-A1 197 30 498, there especially on page 4, lines 13-24, which is hereby expressly the subject of the present disclosure by reference.
  • R 25 represents an optionally substituted aryl group
  • R 26 is an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted benzoyl group, preferably of the formula R 25 - (CO) -.
  • benzoyl peroxide 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, di- (tert-butylperoxy) isophthalate, di- (tert-butylperoxy) terephthalate, di (tert-butylperoxy) phthalate, 2.5- Dimethyl di- (benzoylperoxy) -hexane and 3,3 ', 4,4'-tetra- (tert-butylperoxycarbonyl) -benzophenone.
  • Suitable pyridine N-oxides are described, for example, in DE-A1 197 30 498, there in particular on page 3, lines 44-62, which is hereby expressly the subject of the present disclosure by reference.
  • R 27 , R 28 , R 29 , R 30 or R 31 each independently represent a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted aryl group, R 32 represents an optionally substituted alkyl group and
  • AnC "means an anion.
  • Preferred anions AnC " are BF 4 " , PF ⁇ “ , AsF ⁇ “ , SbF ⁇ “ , CIO 4 “ , Cl “ , Br, tetraphenylborate, tetrakis (pentafluorophenyl) borate, the benzenesulfonate anion, the p-toluenesulfonate anion and the trifluoromethanesulfonate anion.
  • Suitable halomethyltriazines are described, for example, in DE-A1 197 30 498, there in particular on page 4, lines 25-40, which is hereby expressly the subject of the present disclosure by reference.
  • R 33 , R 34 and R 35 each independently represent a trihalomethyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group, with the proviso that at least one of the groups is a trihalomethyl group.
  • 2,4,6-tris (trichloromethyl) -s-triazine 2,4,6-tris (tribromomethyl) s-triazine, 2,4-bis (dichloromethyl) -6-trichloromethyl-s-triazine , 2-propionyl-4,6-bis- (trichloromethyl) -s-triazine, 2-benzoyl-4,6-bis (trichloromethyl) -s-triazine, 2- (4-cyanophenyl-4,6-bis-) (trichloromethyl) -s-triazine, 2- (4-nitrophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-chlorophenyl-4,6-bis (trichloromethyl) -s-triazine , 2- (4-Cumenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-amin
  • the mixture may contain at least one solvent (C).
  • esters such as e.g. Butyl acetate or ethyl acetate, aromatic or (cyclo) aliphatic hydrocarbons, e.g. Xylene, toluene or heptane, ketones, e.g. Acetone, isobutyl methyl ketone, methyl ethyl ketone or cyclohexanone, alcohols such as e.g. Ethanol, isopropanol, mono- or lower oligoethylene or -propylene glycols, mono- or di-etherified ethylene or propylene glycol ethers, glycol ether acetates, such as e.g. Methoxypropylacetat, cyclic ethers such as tetrahydrofuran, carboxylic acid amides such as dimethylformamide or N-methylpyrrolidone and / or water.
  • esters such as e.g.
  • Preferred mixtures according to the invention consist of at least one component (A) of the formula V m An m - Cya + as indicated above, at least one component (B), preferably of the formula (XI), with a counterion V x Kat x + , and if appropriate at least one solvent (C).
  • the mixtures according to the invention are used without solvent (C).
  • the weight ratio between component (A) of the formula V m to m " Cya + and component (B) of the formula (XI) with counterion V x Kat x + in the mixtures according to the invention is preferably 1: 1 to 1: 5, particularly preferably 1: 1 to 1: 4, most preferably 1: 2 to 1: 4.
  • the mixtures according to the invention are readily soluble in coating compositions.
  • the solubility can be influenced by the choice of the anion and the substituents on the cation. Longer alkyl chains than groups R 10 , R 11 or R 12 or as substituents on cyanine generally also lead to better solubility.
  • the sensitizer dyes according to the invention generally have absorption maxima in the NIR wavelength range from 700 nm to 1200 nm and / or in the visible wavelength range from 340 to 700 nm, preferably more than 400 to 700 nm, preferably in the NIR wavelength range.
  • the absorption maximum of the sensitizer color Stoffes can be influenced by the skilled worker in a manner known in principle by the choice of substituents on Cyaninkation.
  • the visible or NIR radiation used for photocuring can be both broadband radiation, such as light-emitting diodes (LED), halogen lamps, Xe lamps, etc. It can also be narrow-band radiation or laser radiation of a specific wavelength. Particularly suitable lasers are the known lasers emitting in the visible and / or NIR range, for example semiconductor diode lasers. The radiation can be fed continuously or pulsed, for example in the form of flashes.
  • Another object of the present invention are radiation-curable coating compositions containing the mixtures of the invention.
  • Such coating compositions typically contain
  • At least one reactive diluent (E) is preferably at least one reactive diluent (E),
  • Binders (D) are compounds with free-radically or cationically polymerizable ethylenically unsaturated groups.
  • the radiation-curable composition preferably contains from 0.001 to 12, particularly preferably from 0.1 to 8, and very particularly preferably from 0.5 to 7, moles of radiation-curable ethylenically unsaturated groups per 1000 g of radiation-curable compounds.
  • (meth) acrylate compounds such as polyester (meth) acrylates, polyether (meth) acrylates, urethane (meth) acrylates, epoxy (meth) acrylates, carbonates (meth) acrylates, silicone (meth) acrylates, acrylated polyacrylates.
  • At least 40 mol%, more preferably at least 60%, of the radiation-curable ethylenically unsaturated groups are (meth) acrylic groups.
  • the radiation-curable compounds can be present, for example, as a solution, for example in an organic solvent or water, as an aqueous dispersion or as a powder.
  • the radiation-curable compounds and thus also the radiation-curable compositions are preferably free-flowing at room temperature. However, it may also be advantageous to apply the radiation-curable compound or the coating composition in the form of a melt or as a powder (powder coating).
  • the radiation-curable compositions preferably contain less than 20% by weight, in particular less than 10% by weight, of organic solvents and / or water. They are preferably solvent-free and anhydrous (so-called 100% systems). In this case, it is preferable to dispense with a drying step.
  • Reactive diluents (E) are, for example, esters of (meth) acrylic acid with alcohols having from 1 to 20 carbon atoms, e.g. Methyl (meth) acrylate, (meth) acrylic acid ethyl ester, butyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl ester, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, dihydrodicyclopentadienyl acrylate, vinyl aromatic compounds, e.g. Styrene, divinylbenzene, ⁇ , ⁇ -unsaturated nitriles, e.g.
  • esters of (meth) acrylic acid with alcohols having from 1 to 20 carbon atoms e.g. Methyl (meth) acrylate, (meth) acrylic acid ethyl ester, butyl (meth) acrylate, (meth) acrylic acid 2-ethylhex
  • N-vinylacetamide, N-vinyl-N-methylformamide and N-vinyl-N-methylacetamide or vinyl ethers e.g. Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, 4-hydroxybutyl vinyl ether, and mixtures thereof.
  • (Meth) acrylic acid in this specification stands for methacrylic acid and acrylic acid, preferably for acrylic acid.
  • UV photoinitiators (F) can be photoinitiators known to those skilled in the art, e.g. those in Advances in Polymer Science, Volume 14, Springer Berlin
  • Suitable examples are phosphine oxides, benzophenones, ⁇ -hydroxy-alkyl aryl ketones, thioxanthones, anthraquinones, acetophenones, benzoins and benzoin ethers, ketals, imidazoles or phenylglyoxylic acids and mixtures thereof.
  • Phosphine oxides are, for example, mono- or bisacylphosphine oxides, as described, for example, in US Pat. EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6 trimethylbenzoylphenylphosphinate or bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide,
  • Benzophenones are, for example, benzophenone, 4-aminobenzophenone, 4,4'-bis (dimethylamino) benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, Michler's ketone, o-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2
  • ⁇ -hydroxyalkyl-aryl ketones are 1-benzoylcyclohexan-1-ol (1-hydroxycyclohexyl-phenylketone), 2-hydroxy-2,2-dimethylacetophenone (2-hydroxy-2-methyl-1-phenylpropane-1-one), 1-hydroxyacetophenone, 1 - [4-
  • xanthones and thioxanthones are 10-thioxanthenone, thioxanthen-9-one, xanthen-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone or chloroxanthenone .
  • Anthraquinones are, for example, ⁇ -methylanthraquinone, tert-butylanthraquinone, anthraquinonecarboxylic acid ester, benz [de] anthracen-7-one, benz [a] anthracene-7,12-dione, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone , 1-chloroanthraquinone or 2-amylanthraquinone,
  • Acetophenones are, for example, acetophenone, acetonaphthoquinone, valerophenone, hexanophenone, ⁇ -phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, p-diacetylbenzene, 4'-methoxyacetophenone, ⁇ -tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 3-acetylphenanthrene, 3-acetylindole, 9-fluoronenone, 1-indanone, 1, 3,4-triacetylbenzene , 1-acetonaphthone, 2-acetonaphthone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 2,2-diethoxy
  • Benzoins and benzoin ethers are, for example, 4-morpholinodeoxybenzoin, benzoin, benzoin isobutyl ether, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether or 7-H-benzoin methyl ether or
  • Ketals are, for example, acetophenone dimethyl ketal, 2,2-diethoxyacetophenone, or benzil ketals, such as benzil dimethyl ketal.
  • Phenylglyoxylic acids are described, for example, in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.
  • photoinitiators are, for example, benzaldehyde, methyl ethyl ketone, 1-naphthaldehyde, triphenylphosphine, tri-o-tolylphosphine or 2,3-butanedione.
  • Typical mixtures include, for example, 2-hydroxy-2-methyl-1-phenylpropan-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-hydroxycyclohexyl phenyl ketone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide and 1-hydroxy cyclohexylphenylketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzophenone and 4-methylbenzophenone or 2,4, 6-trimethylbenzophenone and 4-methylbenzophenone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • At least one UV photoinitiator is present in the coating compositions according to the invention.
  • Colorant (G) is used in the sense of this document summarized for pigments and dyes, preferably for pigments.
  • Pigments (G) are according to CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995 with reference to DIN 55943 particulate "in the application medium practically insoluble, inorganic or organic, colored or achromatic colorants".
  • practically insoluble means a solubility at 25 ° C. of less than 1 g / 1000 g of application medium, preferably less than 0.5, more preferably less than 0.25, very preferably less than 0.1 and in particular less than 0.05 g / 1000 g of application medium.
  • pigments in the true sense include any systems of absorption and / or effect pigments, preferably absorption pigments.
  • Number and selection of the pigment components are not subject to any restrictions. They can be adapted to the respective requirements, for example the desired color impression, as desired. For example, all the pigment components of a standardized mixed-paint system can be based.
  • Effect pigments are to be understood as meaning all pigments which have a platelet-like structure and impart special decorative color effects to a surface coating.
  • the effect pigments are, for example, all effect pigments which can usually be used in vehicle and industrial coating.
  • Examples of such effect pigments are pure metal pigments; such as. Aluminum, iron or copper pigments;
  • Interference pigments such as e.g. titanium dioxide coated mica, iron oxide coated mica, mixed oxide coated mica (e.g., with titanium dioxide and Fe2O3 or titanium dioxide and O2O3), metal oxide coated aluminum, or liquid crystal pigments.
  • the coloring absorption pigments are, for example, customary organic or inorganic absorption pigments which can be used in the coatings industry.
  • organic absorption pigments are azo pigments, phthalocyanine, quinacridone and pyrrolopyrrole pigments.
  • inorganic absorption pigments are iron oxide pigments, titanium dioxide and carbon black.
  • Dyes are also colorants and differ from the pigments by their solubility in the application medium, ie they have at 25 0 C, a solubility above 1 g / 1000 g in the application medium.
  • dyes examples include azo, azine, anthraquinone, acridine, cyanine, oxazine, polymethine, thiazine, triarylmethane dyes. These dyes may find application as basic or cationic dyes, mordant, direct, disperse, development, vat, metal complex, reactive, acid, sulfur, coupling or substantive dyes.
  • additives for example, antioxidants, stabilizers, activators (accelerators), fillers, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents can be used.
  • antioxidants for example, antioxidants, stabilizers, activators (accelerators), fillers, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents
  • stannous octoate, zinc octoate, dibutyltin laureate or diaza [2.2.2] bicyclooctane can be used as accelerators for the thermal aftercuring.
  • photochemically and / or thermally activatable initiators for example potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobisisobutyronitrile, cyclohexylsulfonyl acetyl peroxide, diisopropyl percarbonate, tert-butyl peroctoate or benzopinacol, as well as, for example, those thermally activatable initiators having a half life of 80 0 C of more than 100 hours, such as di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, silylated pinacols, the z.
  • photochemically and / or thermally activatable initiators for example potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-ter
  • ADDID 600 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.
  • chelating agents e.g. Ethylenediaminetic acid and its salts and ß-dike tone be used.
  • Coloriferous inert fillers are understood as meaning all substances / compounds which on the one hand are coloristically inactive; ie show a low intrinsic absorption and their refractive index is similar to the refractive index of the coating medium, and on the other hand are able to influence the orientation (parallel orientation) of the effect pigments in the surface coating, ie in the applied paint film, also properties of the coating or the Coating compositions, for example hardness or rheology.
  • examples of usable inert substances / compounds are mentioned, but without limiting the term coloristically inert topology-influencing fillers to these examples.
  • Suitable inert fillers can be, for example, transparent or semitransparent fillers or pigments, for example plastic granules, silica gels, blancfixe, kieselguhr, talc, calcium carbonates, lime, kaolin, barium sulfate, magnesium silicate, aluminum silicate, crystalline silica, amorphous silica or aluminum oxide.
  • any solid inert organic particles such as, for example, urea-formaldehyde condensation products, micronized polyolefin wax and micronized amide wax, can be used.
  • the inert fillers can also be used in each case in a mixture. Preferably, however, only one filler is used in each case.
  • Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole 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-tetramethyl-4-piperidyl) sebacinate be used. Stabilizers are usually used in amounts of 0.1 to 5.0 wt .-%, based on the solid components contained in the preparation.
  • 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-tetramethyl-4-piperidyl) sebacinate be used.
  • the blends of the present invention are useful as NIR and / or visible light activatable photoinitiators and exhibit better solubility in coating compositions and coating systems than the prior art formulations of NIR photoinitiators in which borate ions of formula (XI) Counterion for the cyanine cation act.
  • This has the consequence that on the one hand the photoinitiator can be distributed more uniformly in the paint system and in the later paint no undissolved particles remain as defects and on the other hand results in a higher photoreactivity.
  • the compounds precipitate partly as crystals in the coating composition due to the lack of solubility.
  • the mixtures according to the invention are mixed with radiation-curable compounds, that is, for example, binders (D) and / or reactive diluents (E) or preparations containing them, for example coating compositions, lacquers or lacquer formulations.
  • radiation-curable compounds that is, for example, binders (D) and / or reactive diluents (E) or preparations containing them, for example coating compositions, lacquers or lacquer formulations.
  • radiation-curable compounds having at least one component (A) of the formula V m to m "Cya + as defined above can, if appropriate, diluted in a solvent, and separately with at least one component (B) of formula (Xl) with a counterion V x Kat x + , if appropriate diluted in a solvent, the solution in a solvent can preferably be dispensed with if the colinitiators are liquid.
  • mixing takes place.
  • a mechanical stirrer for example disc, angled blade, anchor, intensive or gassing, but also by pumping, optionally by a slit, or in a mixing pump, or often by a simple mixture of the two components by hand or by shaking.
  • mixing techniques with higher shear energy such as. Beam dispersion, intensive, Ultraturrax- or ultrasonic dispersion, can be used.
  • photoinitiators of this type also initiate a free-radical polymerization in pigmented paints. Since the activating radiation is usually not or only slightly absorbed by pigments, whereas the required for the activation of UV photoinitiators UV radiation is usually absorbed and / or scattered by the pigments and therefore has a low penetration depth into the coating , Thus, it is a preferred embodiment of the present invention to use the mixtures according to the invention in pigmented coating compositions.
  • a further advantageous embodiment of the present invention is to use the mixtures according to the invention in coating compositions with high layer thicknesses.
  • the coating compositions may have a thickness of up to 300, preferably up to 250 and more preferably up to 200 microns.
  • the coatings can also be applied thicker or thinner, for example from 10 to 1000 microns. However, it may be necessary to irradiate several times with very thick applied coating compositions.
  • the radiation-curable coating composition may preferably be prepared in a simple manner, e.g. by spraying, trowelling, brushing, knife coating, brushing, rolling, rolling, pouring, dipping, laminating, back-molding or coextruding, etc. are applied to the object to be coated and optionally dried.
  • irradiation with electromagnetic radiation takes place, which comprises the visible and NIR range, preferably the NIR range and particularly preferably with electromagnetic radiation in the wavelength range from 700 to 900 nm.
  • the irradiation can also be carried out in the absence of oxygen.
  • the irradiation is carried out so that the coating composition is exposed to an oxygen partial pressure of less than 18 kPa at the moment of its irradiation with NIR radiation.
  • the relevant areas are the surface areas of the object to be coated provided with the radiation-curable coating compositions at the moment of exposure.
  • the oxygen partial pressure is not more than 17 kPa, more preferably not more than 15.3 kPa, most preferably not more than 13.5 kPa, especially not more than 10 kPa and especially not more than 6.3 kPa.
  • oxygen partial pressure preferably 0.5 kPa, more preferably 0.9 kPa, most preferably 1, 8 kPa and especially 2.5 kPa need not fall below.
  • Such a low oxygen partial pressure can advantageously be achieved by diluting the oxygen-containing atmosphere with at least one inert gas or replacing it with at least one inert gas, ie gases which are unreactive under the radiation curing conditions.
  • Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide or combustion gases.
  • the proportion of the at least one inert gas should be more than 80% by volume, preferably at least 85, particularly preferably at least 90, very particularly preferably at least 95 and in particular at least 98% by volume.
  • the irradiation can be carried out by covering the coating mass with transparent media.
  • Transparent media are z. Plastic films, glass or liquids, e.g. Water.
  • the irradiation is particularly preferably carried out as described in WO 01/14483, to which reference is hereby made in its entirety. Very particular preference is given to irradiation in the manner described in DE-A1 199 57 900, to which reference is hereby made in its entirety.
  • the coating compositions and paint formulations according to the invention are particularly suitable for coating substrates such as wood, preferably pine, spruce, beech, oak or maple wood, paper, cardboard, textile, leather, leather substitutes, fleece, plastic surfaces, preferably SAN, PMMA , ABS, PP, PS, PC or PA (abbreviated to DIN 7728), glass, ceramics, mineral building materials, such as cement blocks and fiber cement boards, or metals or coated metals, preferably of plastics or metals, which may for example be present as films ,
  • the metal or coated metal may for example also be shaped for storage or transport to rolls, so-called "coils".
  • the coating of metals may include conventional primer coatings or cathodic dip coating.
  • the coating compositions according to the invention are particularly preferably suitable for exterior coatings or in applications which are exposed to daylight, preferably of buildings or building components, interior coatings, coatings on vehicles and aircraft.
  • the coating compositions according to the invention are used as or in automotive clearcoat and topcoats and in paints, in particular facade paints, industrial coatings, coil coatings, moldings, castings or dental compositions.
  • the coating compositions of the invention as radiation-curable adhesives.
  • Dual cure systems are characterized by being curable by two independent curing mechanisms, e.g. in addition to the radiation still moisture, oxidative or thermal curing.
  • coating compositions of the invention in printing processes or for the production of printing plates, for example in stereolithography, photolithography, screen printing, offset, planographic printing, gravure printing or high-pressure processes, as well as in the inkjet process (ink-jet).
  • Another object of the present invention is the preparation of the co-initiator mixtures according to the invention.
  • the boranate salts of the formula (XI) are usually prepared by reacting a trisubstituted borane with a metallated, usually lithiated or Grignard compound of the fourth substituent, so that the boranate salt of the formula (XI) is initially obtained as metal salt.
  • this metal borohydride is now mixed with at least equimolar amounts of a halide, preferably of the chloride, bromide or iodide, more preferably the chloride or iodide and most preferably the iodide, of the cation Kat x + with respect to the amount of metal ions, then the metal halide is largely precipitated insoluble solid from the formed complex of Kat x + and boranate. Since this complex of Kat x + and boranate according to the invention has a low melting point, the precipitated metal halide can be easily separated by heating above the inventive melting point of the molten complex by a solid-liquid separation, for example filtration, decantation, centrifugation, preferably by filtration. If necessary, the filter residue can still be washed with a suitable solvent.
  • a halide preferably of the chloride, bromide or iodide, more preferably the chloride or iodide and most preferably the iodide, of the
  • the metal halide would have to be purified by selective washes or even by elaborate fractional crystallization. This is significantly simplified by the method according to the invention.
  • the complex of Kat x + and boranate thus obtained according to the invention has a content of metal ions, in particular magnesium or lithium, of less than 1000 ppm, preferably less than 500 ppm, particularly preferably less than 300 ppm, completely more preferably less than 200 ppm, in particular less than 100 ppm and especially less than 50 ppm.
  • the precipitate was distilled in 220 ml. Water dissolved. A solution of 22 g of ethyl iodide quaternized diamine (terminally aminated mixture of tri- and tetra- propylene glycol) in 50 ml of dist. Water was added dropwise within a few minutes. After two hours was filtered off with suction, three times with 20 ml of dist. See water. The residue was dissolved in 300 ml of dichloromethane, dried with sodium sulfate and the solvent was distilled off. The residue was dried at 50 ° C. under reduced pressure for 12 h. This gave 26 g of an oil.
  • ethyl acetate (EE) was used, which has a similar Liehe polarity as typical acrylates, as well as commercially available radically polymerisable lacquer raw materials of the acrylate type (Laromer ® LR 8863 (polyether acrylate based on ethoxylated trimethylolpropane), Laromer ® LR 8987 (urethane acrylate based on hexamethylene diisocyanate as a solution in hexanediol diacrylate) and Laromer ® PO84F LR (amine-modified polyether based on alkoxylated trimethylolpropane), BASF Aktiengesellschaft, Ludiwgshafen).
  • Laromer ® LR 8863 polyether acrylate based on ethoxylated trimethylolpropane
  • Laromer ® LR 8987 urethane acrylate based on hexamethylene diisocyanate as a solution in
  • 0.55 g of the coinitiator C1 according to the invention dissolve in 0.5 ml of EA; 0.1 g of the comparative co-initiator B 1 does not dissolve in 5 ml of EA; 0.1 g of the comparative co-initiator B 1 dissolve in 9 ml of EA.
  • the coinitiators C1, C2 and C3 according to the invention were completely dissolved in the coating raw material. Already after an exposure time of 4 seconds, a hard, clear paint film without specks was obtained.
  • Co-initiators B1, B2 and B3 which are not according to the invention are treated as in the examples according to the invention. There were paint films with specks in the paint obtained.
  • the coating films obtained with the coinitiators according to the invention show better properties than those obtained with the noninventive invention.

Abstract

L'invention concerne des matières de revêtement durcissables par rayonnement, contenant des photoinitiateurs en proche infrarouge. L'invention concerne également de nouvelles formulations de photoinitiateurs en proche infrarouge et leur utilisation.
PCT/EP2007/062049 2006-11-17 2007-11-08 Matières de revêtement durcissables par rayonnement WO2008058885A2 (fr)

Applications Claiming Priority (2)

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EP06124315.0 2006-11-17

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WO2008058885A3 WO2008058885A3 (fr) 2008-07-31

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Publication number Priority date Publication date Assignee Title
DE102013009135A1 (de) 2013-05-31 2014-12-04 Heidelberger Druckmaschinen Ag NIR-vernetzbare Druckfarbe
EP3067218A1 (fr) * 2015-03-13 2016-09-14 Eternit AG Impression à jet d'encre sur des produits en fibrociment

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0408322A1 (fr) * 1989-07-10 1991-01-16 The Mead Corporation Complexes colorant-borate
DE19730498A1 (de) * 1996-07-16 1998-01-22 Showa Denko Kk Lichthärtende Zusammensetzung und Härtungsverfahren hierfür
DE102004011347A1 (de) * 2004-03-05 2005-09-29 Basf Ag Druckfarben für den Offset- und/oder Hochdruck mit NIR-Absorbern sowie in Offset- und/oder Hochdruckfarben lösliche NIR-Absorber
WO2006058731A2 (fr) * 2004-12-03 2006-06-08 Basf Aktiengesellschaft Substance de revetement durcissable au rayonnement

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0408322A1 (fr) * 1989-07-10 1991-01-16 The Mead Corporation Complexes colorant-borate
DE19730498A1 (de) * 1996-07-16 1998-01-22 Showa Denko Kk Lichthärtende Zusammensetzung und Härtungsverfahren hierfür
DE102004011347A1 (de) * 2004-03-05 2005-09-29 Basf Ag Druckfarben für den Offset- und/oder Hochdruck mit NIR-Absorbern sowie in Offset- und/oder Hochdruckfarben lösliche NIR-Absorber
WO2006058731A2 (fr) * 2004-12-03 2006-06-08 Basf Aktiengesellschaft Substance de revetement durcissable au rayonnement

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WO2008058885A3 (fr) 2008-07-31

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