MXPA99008508A - PHOTOACTIVATABLE NITROGEN-CONTAINING BASES BASED ON&agr;-AMINO ALKENES - Google Patents

Abstract

The invention relates to organic compounds having a molecular weight of less than 1000 comprising at least one structural unit of formula (I), in which R1 is an aromatic or heteroaromatic radical which is capable of absorbing light in the wavelength range from 200 to 650 nm and in doing so brings about cleavage of the adjacent carbon-nitrogen bond. The compounds represent photoinitiators for base-catalysable reactions. Other subjects of the invention are base-polymerizable or cross-linkable compositions comprising compounds having a structural unit of formula (I), a method of implementing photochemically induced, base-catalysed reactions, and the use of the compounds as photoinitiators for base-catalysed reactions.

Description

BASES CONTAINING PHOTOACTIVAB NITROGEN, BASED ON a-AMINO ALKENS The invention relates to a-amino alkenes that can be converted photochemically into amidine derivatives, to a process for their preparation and to a process for the photochemical preparation of the amidine derivatives. Additional objects of the invention are crosslinkable or polymerizable base compositions comprising these α-amino alkenes, a method for implementing photochemically induced, base catalyzed reactions, and the use of α-amino alkenes as photoinitiators for base catalyzed reactions. . The photolytic generation of bases and photopolymerization reactions with these bases have already been described, using various types of photolabile compounds, examples are carbamates (Cameron et al., US Patent 5 545 509 and references cited there; Cameron and Frechet, J. Am. Chem. Soc. (1991) 113, 4303), o-keto carbamates (Cameron et al., J. Am. Chem. Soc. (1996), 118, 12925), 0-acyloximes (Tsunooka et al., J. Polymer Sci .: Part A: Polymer Chem. (1994), 32, 2177), formamides (Nishi ubo et al., Polym J. (1993) 25,421; idem, J. Polymer Sci.: Part A: Polymer Chem (1993), 31,3013), co-amine complexes (C. Kutal et al., J. Electroc em. Soc. (1987), 134, 2280).

The elimination reactions of intramolecular photochemical hydride in olefins is known but not well described as the corresponding reactions of carbonyl compounds (see V. Sreedhara Rao, AK Chandra, J. Photoc, Photobiol.A Chem. 101 (1996) , 189 and references cited therein). Corresponding thermal reactions of olefins are much better described for example by J.-L. Ripoll, Yvallée in Synthesis (1993), 659 and references cited therein. Surprisingly, it has now been found that certain α-amino alkenes comprising a structural unit of the formula (I) releases an amidine group when exposed to visible light or UV light. This amidine group is sufficiently basic to initiate a large number of base catalysable reactions, especially polymerization reactions. The compounds are of high sensitivity and through the selection of the R substituent the absorption spectrum can be varied over a wide range.

The compounds make it possible to prepare so-called one-pot systems with base-catalysable oligomers or monomers, which have an extremely long shelf life. A polymerization reaction, for example, starts only after exposure to light. The systems can be formulated with little or no solvent, since the compounds can be dissolved in the monomers or oligomers, without being affected. The active catalyst is formed only after exposure to light. These systems with base catalysable monomers or oligomers can be used for numerous purposes such as for finishes, coatings, molding compounds or photolithographic reproductions. The invention therefore provides organic compounds having a molecular weight less than 1000, comprising at least one structural unit of the formula (I) (I), wherein Rx is an aromatic or heteroaromatic radical capable of absorbing light in the wavelength range from 200 to 650 nm and in so doing achieves breakdown of the adjacent carbon-nitrogen bond. By aromatic or heteroaromatic radicals Rx is understood to mean those that comply with the Hückel Rule 4n + 2. The absorption maxima can be varied within a wide range through the selection of the aromatic or heteroaromatic radical Rx and in this way the photosensitivity of the compounds can move from the UV region to that of daylight. Preference is given to organic compounds wherein the structural unit of the formula (I) comprises compounds of the formula (II) (ll), where x is an aromatic or heteroaromatic radical capable of absorbing light in the wavelength range from 200 to 650 nm and in doing so achieves breakage of the adjacent carbon-nitrogen bond; R2 and R3 independently of each other are hydrogen, alkyl having 1 to 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, alkynyl with 3 to 18 carbon atoms, or phenyl and if R2 is hydrogen or alkyl with 1 to 18 atoms of carbon, R3 is additionally a group -CO-R14 wherein R 14 is alkyl with 1 to 18 carbon atoms or phenyl; Rs is alkyl with 1 to 18 carbon atoms or NR15R16; R4, R6 R7 / R15 and R16 independently of one another are hydrogen or alkyl having 1 to 18 carbon atoms or R4 and R6, together they form an alkylene bridge with 2 to 12 carbon atoms or R5 and R7, independently of R4 and R6, together they form an alkylene bridge with 2 to 12 carbon atoms or if R5 is NRi5R16 / R16 and R7 together form an alkylene bridge with 2 to 12 carbon atoms; R17 is hydrogen or alkyl with 1 to 18 carbon atoms; R18 is hydrogen, alkyl having 1 to 18 carbon atoms or phenyl substituted with alkyl having 1 to 18 carbon atoms, vinyl, alkenyl with 3 to 18 carbon atoms, alkynyl with 3 to 18 carbon atoms, haloalkyl with 1 to 18 carbon atoms, phenyl, N02, OH, CN, OR10, SR10, C (0) Rn, C (0) 0R12 or halogen; and R ?o, Rn and Ri2 are hydrogen or alkyl with 1 to 18 carbon atoms.

Alkyl in the various radicals having up to 18 carbon atoms is a branched or unbranched radical such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethyl-butyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n- octyl, 2-ethexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1, 3, 3, 5, 5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl. Preference is given to alkyl having 1 to 12, especially 1 to 6, carbon atoms. Alkenyl having 3 to 18 carbon atoms is a branched or unbranched radical, such as propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2, 4-pentadienyl, 3-methyl-2-butenyl, n-2 -octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference is given to alkenyl having 3 to 12, especially 3 to 6 carbon atoms. Alkynyl having 3 to 18 carbon atoms is a branched or unbranched radical such as propynyl (-CH2-C = CH), 2-butynyl, 3-butynyl, n-2-octynyl, or n-2-octadecynyl. Preference is given to alkynyl having 3 to 12, especially 3 to 6, carbon atoms.

Examples of alkylene bridges with 2 to 12 carbon atoms are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene or dodecylene. Preference is given to those compounds of formula II wherein R x is phenyl, naphthyl, phenanthryl, anthracyl, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,1,8-tetrahydro-l- naphthyl, thienyl, benzo [b] thienyl, naphth [2, 3-b] thienyl, thiarenyl, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxyntinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, terphenyl, stilbenyl, fluorenyl or phenoxazinyl, these radicals are unsubstituted or substituted one or more times by alkyl with 1 to 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, alkynyl with 3 to 18 carbon atoms, haloalkyl with 1 to 1 8 carbon atoms, N02, NR8R9, N3, OH, CN, OR10, SR10, C (0) Ru, C (0) 0R12 or halogen; or R2 is a radical of formulas A or B R8, R9, R10, Ru and R12 are hydrogen, alkyl having 1 to 18 carbon atoms; R 13 is alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms, alkynyl with 2 to 18 carbon atoms, haloalkyl with 1 to 18 carbon atoms, N 0 2, NR 8 R 9, OH, CN, OR 10, SR 10, C (0) R11, C (O) OR12 or halogen; and n is 0 or a number 1,2 or 3. Examples of alkyl with 1 to 18 carbon atoms, alkenyl with 3 to 18 carbon atoms and alkynyl with 3 to 18 carbon atoms have already been indicated above. Halogen is fluorine, chlorine, bromine or iodine. Examples of haloalkyl with 1 to 18 carbon atoms comprise total or partially halogenated alkyl. The halogen (halo) here is F, Cl, Br or I. Examples are the positional isomers of mono- to deca-fluoropentyl, mono-a-octafluorobutyl, mono- to hexafluoropropyl, mono- to tetrafluoroethyl and mono- and difluoromethyl and also the corresponding chloro, bromo and iodo compounds. Preference is given to perfluorinated alkyl radicals. Examples of these are perfluoropentyl, perfluorobutyl, perfluoropropyl, perfluoroethyl and in particular trifluoromethyl. Examples of the amino group NR8R9 are the respective monoalkyl or dialkylamino groups such as methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, octadecylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamino, di-n-butylamino, di-isobutylamino, dipentylamino, dihexylamino or dioctadecylamine. Additional dialkylamino groups are those in which the two radicals independently are branched or unbranched, for example, methylethylamino, methyl-n-propylamino, methylisopropylamino, methyl-n-butylamino, methylisobutylamino, ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino , ethyl-tert-butylamino, isopropyl-n-butylamino or isopropylisobutylamino. The OR10 alkoxy group having up to 18 carbon atoms is a branched or unbranched radical such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Preference is given to alkoxy having 1 to 12, especially 1 to 8, for example 1 to 6 carbon atoms. Examples of the thioalkyl group SR10 are thiomethyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl, thioheptyl, thiooctyl or thiooctadecyl, it being possible for the alkyl radicals to be linear or branched.

Examples of the radical R1 are phenyl, naphthyl, phenanthryl, anthracyl, biphenylyl, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo [b ] thienyl, naph or [2, 3-b] thienyl, thiarenyl, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxyntinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, I perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, sty-benyl, terphenyl, fluorenyl, phenoxazinyl, methoxyphenyl, 2,4-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 3,4,5-trimethoxyphenyl , bromophenyl, tolyl, xylyl, mesityl, nitrophenyl, dimethylaminophenyl, diethylaminophenyl, aminophenyl, diaminophenyl, thiomethylphenyl, l-naphthyl, 2-naphthyl, 1-phenylamino-4-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, l-methoxy-2 -naphthyl, 2-methoxy-1-naphthyl, 1-dimethylamino-2-naphthyl, 1, 2-dimethyl-4-naphthyl, 1,2-dimethyl-6-naphthyl, 1, 2-dimethyl-7-naphthyl, 1 , 3-dimethyl-6-naphthyl, 1,4-dimethyl-6-naphthyl, 1,5-dimethyl-2-naphthyl, 1,6-dimethyl-2-naphthyl, l-hydroxy-2-naphthyl, 1-hydroxy -l-naphthyl, 1,4-dihydroxy-2-naphthyl, 7-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, 3-benzo [b] thienyl, 5-benzo [b] thienyl, 2-benzoyl [b] thienyl, 4-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl-7-dibenzofuryl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-phenoxathiinyl or, 2, 7-phenoxathiinyl, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4- imidazolyl, 2-ethyl-5-imidazolyl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, l-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2- methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1, 5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2, 7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthridin-2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino- 6-quinazolinyl, 3-cinolinyl, 6-cinolinyl, 7-cinolinyl, 3-meto xi-7-cinolinyl, 2-pteridinyl, 6-pteridinyl, 7-pteridinyl, 6,7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3- carbazolyl, β-carbolin-3-yl, l-methyl-β-carbolin-3-yl, 1-methyl-β-carbolin-6-yl, 3-phenytridinyl, 2-acridinyl, 3-acridinyl, 2-perimidinyl, l-methyl-5-perimidinyl, 5-phenanthrolinyl, 6-phenanthroline, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3- phenothiazinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2-phenoxazinyl or 10-methyl-2-phenoxazinyl. Preferably preferably Rx is phenyl, naphthyl, pyrenyl, thioxanthyl or phenothiazinyl, these radicals are unsubstituted or substituted one or more times by alkyl with 1 to 18 carbon atoms, haloalkyl with 1 to 18 carbon atoms, NR8R9, CN, N02 , N3 SR10, or OR10, or Ri is a radical of the aforementioned formulas A or B. Additional particularly preferred compounds are those wherein R ± is phenyl, pirenyl or naphthyl, unsubstituted or substituted one or more times by CN, NR8R9 , N02r CF3r SR10, or OR10, or Rx is a radical of the aforementioned formulas A or B. Particularly preferably, Rx is phenyl, 4-aminophenyl, 4-methylthiophenyl, 4-trifuloromethylphenyl, 4-nitrophenyl, 2, 4, 6-trimethoxyphenyl, 2,4-dimethoxyphenyl, naphthyl, anthracyl, pyrenyl, or a radical of the formula A or defined above.

R2 'and R3 independently of one another are preferably hydrogen or alkyl having 1 to 6 carbon atoms. It is also preferred that R4 and R6 together are an alkylene bridge with 2 to 6 carbon atoms. Preferably R5 and R7 are an alkylene bridge with 2 to 6 carbon atoms or if R5 is NR15R16? R16 and R7 together are an alkylene bridge with 2 to 6 carbon atoms. Preferably, R17 is hydrogen or alkyl having 1 to 4 carbon atoms and R18 is hydrogen, alkyl having 1 to 4 carbon atoms or phenyl. A particularly preferred group of compounds of formula (II) are those in which Rx is phenyl, naphthyl or pyrenyl, these radicals are unsubstituted or are substituted one or more times by CN, NR8R9, N02, CF3, SR10 or 0R10, or Rx is a radical of formulas A or B as described above; n is 0 and the radicals R8, R9, R10 and R13 are hydrogen or alkyl having 1 to 6 carbon atoms; R2 and R3 are hydrogen or alkyl with 1 to 6 carbon atoms; R4, R6 and R7 independently of one another are hydrogen or alkyl having 1 to 6 carbon atoms; R5 is alkyl with 1 to 4 carbon atoms or NR15R16, wherein Ris and Ri6 sc > n hydrogen or alkyl having 1 to 6 carbon atoms; or K-4 and R6 together form an alkylene bridge with 2 to 6 carbon atoms; or, independently of R4 and R6, R5 and R7 together form an alkylene bridge with 2 to 6 carbon atoms; or, if R5 is NR15R16, R16 and R7 together form an alkylene bridge with 2 to 6 carbon atoms; R17 is hydrogen or alkyl with 1 to 4 carbon atoms; and R18 is hydrogen, alkyl having 1 to 4 carbon atoms or phenyl. Particular preference is given to organic compounds of the formula (II) wherein Rx is phenyl or naphthyl, the phenyl and naphthyl radicals are unsubstituted or substituted one or more times by CN, NR8R9, N02, CF3, SR10 or OR? 0, or R- is tiantrenyl, fluorenyl or thioxanthyl, or Rx is a radical of formula A n is 0 and the radicals R8, R9 and R10 are hydrogen or alkyl having 1 to 6 carbon atoms; R2 and R3 are hydrogen or alkyl with 1 to 6 carbon atoms; R2 and R3 together form an alkylene bridge with 2 to 6 carbon atoms; R5 and R7 together form an alkylene bridge with 2 to 6 carbon atoms; R17 is hydrogen; and R18 is hydrogen or alkyl having 1 to 4 carbon atoms.

The invention further provides a process for preparing compounds having the structural unit of the formula (I) as described above, comprising in a first step, reacting a compound comprising a structural unit of the formula (III) with a compound comprising a structural unit of formula IV wherein Halogen is F, Cl, Br or I and Rx is as defined in claim 1, and, in a second step, carrying out a Wittig reaction using a phosphonium salt, with the reaction product thus obtained. Preference is given to a process for preparing compounds of the formula (II) which comprises reacting a compound of the formula (V) (V) > wherein the radicals R4, R5, R6 and R7 are as defined above, including the preferred meanings, with a compound of the formula VI) wherein the radicals Rx, R2 and R3 are as defined above, including the preferred meanings, and Halogen is F, Cl, Br or I, and in a second step, conducting a Wittig reaction with the reaction product thus obtained, using a phosphonium salt of the formula VII R17R18 CH-P (phenyl) / X ~ (VII), wherein R17 and R18 are as defined above, including the preferred meanings, and X is F, Cl, Br, I or tetrafluoroborate . Suitable Wittig reagents (phosphonium salts) are commercially available and are mentioned, for example, in the Lancaster Chemical Catalog, Appendix 1, pages A2-A6. Examples are: methyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, n-propyltriphenylphosphonium bromide, n-butyltriphenylphosphonium chloride, n-butyltrifenylphosphonium bromide, isobutyltrifenylphosphonium bromide. Onium, n-amyltrifenylphosphonium bromide, isoamylphifenylphosphonium bromide, n-hexyltrifenylphosphonium bromide, bromide @ n-heptyltriphenylphosphonium, n-octyltrifenyl phosphide bromide, n-nonyltrifenylphosphonium bromide, n-decyltrifenylphosphonium bromide, n-undecide bromide and 11-trifluoromethyl bromide, bromide of n -dodecyltrifenylphosphonium, n-tet radecyl trifluorophosphium bromide, n-hexadecyltrifenylphosphonium bromide, trimethylsilylmethyltriphenylphosphonium iodide, 2-dimethylaminoethyl trifluorophosphonium bromide, 2-chloroethyltriphenylphosphonium bromide, bromide 2-Hydroxyethyltriphenylphosphonium, 3-bromopropyltriphenylphosphonium bromide, bromide 4 - . 4 - . 4 - . 4 - . 4 - . 4 - . 4 - . 4-bromobutyltrifenylphosphonium, 2- (1, 3 - . 3 - . 3-dioxan-2-yl) ethyl rif enylphosphonium, cyclopropylmethyl trifluorophosphium bromide, bromide 4 - carboxibu t i 11 r i f eni 1 f osio, bromide 4 - carboethoxybutyl trifluorophosphium, bromide 4 -pentyl enyl trifluorophosium, 5-hexenyl trdLf enylphosphonium bromide, 3-f-enylpropyltrifenylphosphonium bromide, ethylenebis (triphenylphosphonium bromide), bromide-bromide (tri-phenylphosphonium), tetramethylenebis (trifluorophosium bromide), penthamethylbenzene bromide (tri-phenylphosphonium), isopropyltriphenylphosphonium iodide, 2-butyltrifenylphosphonium bromide, 2-methyltrifenylphosphonium bromide, bromide of cyclopentyltrifenylphosphonium, cyclohexyltriphenylphosphonium bromide, cyclohexyl bromide, 11-rifenyl-1-phosphonium, allyltrifenylphosphonium chloride, allyltrifenylphosphonium bromide, aluminum chloride. aliltrif enilf osf onio, 2-methylallyltrifenyl phosphonium chloride, 3-methylalyxtriphexylphosphonium, 3,3-dimethyl thiol trifluoride bromide, 2-bu en-1,4-bis (trifluorophosphium) chloride, citamyl chloride enilf osf onium, cinnamyltrimethylphosphonium bromide, propargyltrifenylphosphonium bromide, benzyltrifenylphosphonium chloride, benzyltrifenylphosphonium bromide, benzyltrifenylphosphonium iodide, 2-methylene chloride 1 in 11 1 phosphoium, bromide 2-Methylbenzyltrifenylphosphonium, 3-methyl chloride 1 b e n c i 11 r i f e n i f o f o s, chloride 4 - me t i lbenc i 11 r i f eni 1 s f oni o, 4-methylbenzyltrifenylphosphonium bromide, 2-hydroxybenzyltrifenylphosphonium bromide, 4-me toxibencyl trifluoride, phosphonium bromide, bromide 4-ethoxybenzyltrifenylphosphonium, 4-butoxybenzyl bromide 11 r i f in i 1 f o s f o n, chloride 4-Fluorobenzyltrifenylphosphonium, 4-C 1 -chloride or r ob e n c i 1 t r i f e i f o n f o n i, bromide 4-bromobenzyltrifenylphosphonium, 4-cyanobenzyl trifluorophosphonium chloride, 4-carbomethoxybenzyltrifenylphosphonium bromide, hydrate bromide 2 - . 2-nitrobenzyl trifluorophosphium, bromide of 4-nitr or 1-trifluoro-1-phosphonium, o-xylylene bis (trifluorophosphium) bromide, p-xylylenebis (trifluorophosphium) chloride, bromide p-xylylenebis (triphenylphosphonium), chloride 1 - . 1-naphthylmethyltriphenylphosphonium chloride benzhydryltriphenylphosphonium, hydroxymethyltriphenylphosphonium chloride, methoxymethyltriphenylphosphonium chloride, chloromethyltriphenylphosphonium iodide, methylthiomethyltriphenylphosphonium chloride, 1-phenylthiomethyltrifenylphosphonium chloride, 1,3-dithian-2-yltrifenylsium chloride, formylmethyltrifenylphosphonium chloride, chloride of acetonyltrifenylphosphonium, acetonyltrifenylphosphonium bromide, f-enacyltrifenilf osphonium bromide, demethyl bromide, 1-trifluoride trifluoride, carbomethoxymethyl trifluorophosphonium, carbomethoxymethylmethyl trifluoride fos ph onium, carboet oxymethyl thi phenyl phosphonium chloride, carboethoxymethyltrifenylphosphonium bromide, 1-carboethoxyethyltrifenylphosphonium bromide, methyl bromide 4- (trifluorophosphonate) crotonate, tetraf luoroborate. of 1-carboethoxycyclopropyltrifenylphosphonium, cyanomethyl chloride, phosphonium, 2- (trifluorophosphonanilidene) succinic anhydride, bromide 9 -. 9 - f 1 u or r e n i 11 r i f e n i 1 f o s f on i o, vinyltrifenylphosphonium bromide, or bromide (1,2-vinylenebis (triphenylphosphonium) The reaction of compounds having the formula (V) with compounds having the formula VI) can be conducted in a manner known per se. Advantageously, a solvent or mixture of solvents is used, examples are hydrocarbons such as benzene, toluene, xylene, etc., halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, etc., alkanols such as methanol, ethanol , ethylene glycol monomethyl ether, etc., and ethers such as diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, etc., and mixtures of said solvents.

The reaction can be conducted judiciously within a temperature range from -10 ° C to 100 ° C. Preference is given to reaction temperatures from 10 ° C to 50 ° C. The Wittig reaction can be carried out in a conventional manner. It is advantageous to employ a solvent or mixture of solvents, e.g. hydrocarbons such as benzene, toluene, xylene, etc., halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, etc., alkanols such as methanol, ethanol, ethylene glycol monomethyl ether, etc. and ethers such as diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, etc. and mixtures of those solvents. The reaction can be conducted within a temperature range from -10 ° C to 100 ° C. Preference is given to reaction temperatures from 10 ° C to 70 ° C. In the course of preparing the photolatent bases of the invention it is possible that mixtures of isomers are formed. These can be separated by familiar methods familiar to the person with dexterity. Alternatively, it is possible to employ the particular resulting isomer mixtures directly as photolatent bases. The invention further provides a process for preparing a compound of the formula (VII) R7 N (Vil), Rr R < wherein R4, R5, R6 and R7 are as defined above, including their preferred meanings, which comprises exposing a compound of the formula (II) wherein the radicals R1, R3, R3, R4, R5, R6, R7, R17 and R18 are as defined above, including their preferred meanings, to light having a wavelength from 200 nm to 650 nm. The reaction is conveniently carried out in a solvent or mixture of solvents. The concentration of the compounds of the formula (II) is advantageously adjusted so that virtually all the light is absorbed in the reaction vessel. The reaction solution is preferably stirred and, if desired, cooled in the course of exposure. Suitable solvents are those listed above.

According to the invention, the organic compounds comprising a structural unit of the formula I can be used as photolatent bases. The invention therefore further provides a composition comprising A) at least one compound that '> • .2 a structural element of formula (I) and B) at least one organic compound capable of substitution reaction or base-catalyzed addition. Preference is given to the organic compounds of the formula 'II) described above. The base-catalyzed substitution or addition reaction can be carried out with compounds of low molecular mass (monomers) with oligomers, with polymeric compounds or with a dt. os, '-stos. Examples of reactions that can be carried out both with monomers and with oligomers / polymers using the novel photoinitiators are the Knoevenagel reaction or the Michael addition reaction. D (particular importance are compositions wherein component B) is an organic material crosslinkable or anionically polymerizable. The organic material may be in the form of monomers, oligomers or polymers: mono 1 li-functionali s.

Particularly preferred oligomeric, -? .mericu systems are customary in the coating industry. Examples of these binders or base catalysable coating systems are: a) acrylate copolymers having alkoxysilane or alkoxysiloxane side groups, for example the polymers described in US-A 4,772,672 or US-A 4,444,974; b) two-component systems comprising polyacrylates containing hydrnxyl groups, polyesters and / or polyethers and polyisocyanamics or aromatics, c) two-component systems comprising functional polyacrylates and a polyepoxide, wherein the polyacrylate contains carboxyl or anhydride; d) two-component systems comprising polyacrylates, polyesters and / or polyethers containing hydroxyl groups modified with silicone or modified with fluorine and aliphatic or aromatic polyisocyanates, e) two-component systems comprising (poly) ketimines and polyisocyanilic acids or aromatics; f) two-component systems comprising (poly) ketimines and unsaturated acrylate resins or acetoacetate or methyl a-acrylamidomethylglycolate resins; h) two-component systems comprising (poly) oxazolidines and polyacrylates containing anhydride groups or unsaturated acrylate resins or polyisocyanates; i) two-component systems comprising epoxy functional polyacrylates and polyacrylates containing amino group; 1) polymers based on id 1 gli i M ether; m) two-tier systems comprising a (poly) alcohol and a (poly) isocyanate; n) two-component systems comprising a α, β-ethylenically unsaturated carbonyl compound and a polymer containing activated CH 2 groups, it being possible for CH groups "> activated are present either in the main chain or in the secondary chain or in both, as described for example in EP-B-O 161 697 for (poly) malonate groups. Other computations that have activated Cll groups are (poly) acetoaceta 'and (poly) cyanoaceionates. Among these base-catalysable binders, particular preference is given to the following: b) two-component systems comprising polyacrylates, polyesters and / or polyethers containing hydroxyl groups and aliphatic or aromatic polyisocyanates; c) two-component systems comprising functional polyacrylates and a polyol, where polyacrylate contains xyl, anhydride groups; i) two-component systems comprising polyacrylates containing epoxy and polyacrylates containing carboxyl group; m) two-component systems comprising a (poly) alcohol and a (poly) isocyanate; and n) two-component systems comprising a α, β-ethylenically unsaturated carbonyl compound and a polymer containing idlic CFl groups, it being possible for activated CH 2 groups to be present, either in the main chain or in the secondary chain or in both . Two-component systems comprising a α, β-ethylenically unsaturated carbonyl compound and a (poly) malonate, and their preparation, are described in EP-B-0 161 697. The malonate group herein can be connected in a polyurethane, polyester, polyacrylate , epoxy resin, polyamide or polyvinyl polymer, either in the main chain or in a secondary chain. h: The α, β-ethylenically unsaturated carbonyl atom used can be any double bond activated by a carbonyl group. Examples are esters or amides of acrylic acid or methacrylic acid. In the ester groups, it is also possible that additional hydroxyl groups are present. Diesters and triesters are also possible. Typical examples are hexandiol diacrylate or trimethylol propane triacrylate. Instead of acrylic acid, it is also possible to use other acids and their esters or amides such as Protonic acid or cinnamic acid. Under base catalysis, the components of the system react with each other at room temperature to form an interlocking coating system that is suitable for numerous applications. Due to their good resistance to inherent weathering, they are suitable for example for outdoor applications as well and can, if required, be additionally stabilized by UV absorbers and other light stabilizers. Other adequate systems. > s as component B) in the novel compositions are epoxy systems. Epoxy resins which are suitable for preparing novel, curable mixtures comprising epoxy resins as component B) are those which are customary in epoxy resin technology, examples of these epoxy resins are: I) Polyglycidyl and poly (β-methylglycidyl) esters, which they are obtained by reacting a compound having at least two carboxyl groups in the molecule with epichlorohydrin or β-methylepicl. . ihydrin The reaction is carried out judiciously in the presence of bases. Since the compound has at least two carboxyl groups in the molecule, it is possible to use aliphatic polycarboxylic acids. Examples of these polycarboxylic acids are oxalic, succinic, glutaric, adipic, pimelic, suberic, azelaic or dimerized or trimerized linoleic acid. It is also possible, however, to employ cycloaliphatic polycarboxylic acids such as acid t t t t ahydr or f ttal ic, 4-me t i 11 e t r ah i or f t a 1 i c o, hexahydrophthalic or 4-methylhfj >; ' ihidroit? lico. Further aromatic polycarboxylic acids may be used such as phthalic, isophthalic or terephthalic acid. II) Polyglycidyl or poly (β-methylglycidyl) ethers, which are obtained by reacting a compound having at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups with epichlorohydrin or β-methylepichlorohydrin, under alkaline conditions or in the presence of a Acidic catalyst with subsequent alkaline treatment. Glycidyl ethers of this type are derived, for example, from acyclic alcohols such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propan-1,2-diol or poly (oxypropylene) glycols, pr opan - 1, 3 diol, bu t an-1,4-dio 1, poly (oxy-tetramethylene) glycols, pentan-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1, 1, 1-trimethylolpropane, pentaerythritol, sorbitol and polyepichlorohydrins. Also derived, for example, from "cycloaliphatic alcohols" such as 1,4-cyclohexanedimethanol, bis (4-hydroxycyclohexyl) -methyl or 2,2-bis (4-hydroxycyclohexyl) -panoid, or possess aromatic nuclei such as N, N-bis. (2-hydroxyethyl) aniline op, p'-bis (2-Lydroxyethylamino) -diphenylmethane The glycidyl ethers may also be derived from, for example, mononuclear phenols such as resorcinol or hydroquinone, or are based on polynuclear phenols such as bis (4-hydroxyphenyl) ) methane, 4, 4'-dihydroxybiphenyl, bis (4-idroxyphenyl) sulfone, 1, 1,2,? -tetrakis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) -panole, 2,2-bis (3, 5-dibromo-4-hydroxyphenyl) -propane and novolaks obtained by condensing aldehydes such as formaldehyde,? Oetaldehyde, chloral or furfuraldehyde, with phenols such as phenol or with phenols whose nuclei are replaced by chlorine atoms or alkyl groups with 1 to 9 carbon atoms, examples being 4-chlorophenol, 2-methylphenol or 4 -tertbutylphenol or by condensation with bisphenols, those of the type specified above. III) Poly (N-glycidyl) compounds which are obtained by dehydrochlorination of the reaction products of epichlorohydrin with amines containing at least two aromatics of amine hydrogen. These amines, for example, are aniline, n-butylamine, bis (4-aminophenyl) -methane, m-xylylenediamine or bis (4-methylaminophenyl) methane.

The poly (N-glycidyl) compounds also include triglycidyl isocyanurate, N, N 1 -diglycidyl derivatives of cycloalkylene ureas such as ethylene urea or 1,3-propylene urea and diglycidyl derivatives of hydantoins such as 5,5-dimethylhydantoin. IV) Poly (S-glycidyl) compounds, for example di-S-glycidyl derivatives which are obtained from dithiols such as ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether. V) Cycloaliphatic epoxy resins for example bis (2,3-epoxycyclopentyl) ether, 2,3-epoxy-cyclopentyl glycidyl ether, 1,2-bis (2,3-epoxycyclopentyloxy) ethane or 3,4-epoxycyclohexyl-methyl-3 ', 4' -epoxycyclohexanecarboxylate. However, it is also possible to use epoxy resins wherein the 1,2-epoxide groups are connected to different heteroatoms and / or functional groups; These compounds include, for example, the N, N, 0-triglycidyl derivative of 4-aminophenol, the glycidyl ether, the glycidyl ester of salicylic acid, N-glycidyl-N '- (2-glycidyloxypropyl) -5,5-dimethylhydantoin or 2 - glycidyloxy-1,3-bis (5,5-dimethyl-1-glycidylhydantoin-3-yl) propane. Mixtures of epoxy resins can also be used as component B). Also according to the invention, therefore, are compositions containing as component B), an epoxy resin or a mixture of different epoxy resins.

The compositions comprise the photoinitiator, component A), preferably in an amount of 0.01 to 10% by weight, based on component B). In addition to the photoinitiator, component A), the photopolymerizable mixtures may include different additives. Examples of these are thermal inhibitors which are intended to avoid premature polymerization, such as hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol or sterically hindered phenols, such as 2,6-di (tert-butyl) -p-cresol, for example. To increase storage stability in the dark, it is possible for example to use copper compounds, such as copper naphthenate, stearate or octoate, phosphorus compounds such as triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzyl phosphite, compounds of quaternary ammonium, such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives such as N-diethylhydroxylamine. To exclude atmospheric oxygen during polymerization, it is possible to add paraffin or similar wax-like substances that, due to their lack of solubility in the polymer, migrate to the surface at the beginning of the polymerization where they form a transparent surface layer that prevents the entry of air . It is also possible to apply an oxygen impermeable layer.

Light stabilizers, which can be added in a small amount, are UV absorbers, such as those for example of the hydroxyphenylbenzotriazole, hydroxyphenylbenzophenone, oxalamide or hydroxyphenyl-s-triazine type. Individual compounds or mixtures of these compounds can be used with or without the use of sterically hindered amines (HALS). Examples of these UV absorbers and light stabilizers are the following: 1. 2- (2'-Hydroxyphenyl) benzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2-51-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3 -tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5) '-methylphenyl) -5-chloro-benzotriazole, 2- (3' -sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5' -di-ter-amyl-2'-hydroxyphenyl) -benzotriazole, 2- (31, 5'-bis- (, -dimethylbenzyl) -2'-hydroxy-phenyl) benzotriazole, a mixture of 2 - (3'-tert-butyl-2'-hi-di-oxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhex.yloxy) carbonylethyl] -2-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonyl-ethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5) '- [2- (2-ethexyloxy) carbonylethyl] -2'-hydroxy-phenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) -benzotriazole and 2- (' -ter) -butyl-2 '-hydroxy-5' - (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the transesterification product of 2 - [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO (CH2) 3] 2- where R = 3'-tert-butyl-4 '-hydroxy-5'-2H-benzotriazol-2-ylphenyl. 2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4'-trihydroxy and 2'-hydroxy-4 derivatives , 4'-dimethoxy. 3. Esters of substituted and unsubstituted benzoic acids, such as for example 4-tert-butyl-phenyl &alicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-diols tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxy-benzoate and 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxy-benzoate. 4. Acrylates, for example ethyl or isooctyl a-cyano-β, β-diphenylacrylate, methyl a-carbometpxi-cinnamate, methyl and butyl a-cyano-β-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-methoxy cinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline. 5. Sterically hindered amines, for example bis (2, 2, 6, 6-tetramethyl-piperidyl) sebacate, bis (2, 2,6,6-tetramethyl-piperidyl) succinate, bis (1, 2,2,6, 6-pentamethyl-piperidyl) -sebacate, bis (1,2-, 2,6,6,6-pentamethyl-piperidyl) n-butyl-3, 5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1- (hydroxyethyl) -2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate of N, N'-bis (2, 2, 6,6-tetramethyl-4-piperidyl) hexa-methylenediamine and -ter-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl- 4-piperidyl) -1,2,3,4-butane-tetraoate, 1, 1 '- (1, 2-ethanedyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6 , 6-tetramethyl-piperidine, bis (l, 2,2,6,6-pentamethylpiperidyl) -2-n-butyl -2 - (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n -octyl-7,7,9, 9- tetramethyl-1, 3,8-triazaspiro [4.5] decan-2,4-dione, bis (1-octyloxy-2, 2,6,6-tetramethylpiperidyl) sebacate, bis (l-octyloxy-2,6,6,6-tetramethylpiperidyl) succinate, the condensate of N, N'-bis (2, 2, 6,6-tetramethyl--piperidyl) hexamethylenediamine and 4-morpholine-2,6- dichloro-l, 3, 5-triazine, the condensate of 2-chloro-4,6-bis (4-n-butylamino-2, 2,6,6-tetramethylpiperidyl) -1, 3, 5-triazine and 1, 2-bis (3-amino-propylamino) ethane, the condensate of 2-chloro-4,6-di- (4-n-butylamino-l, 2, 2,6,6-pentamethylpiperidyl) -1, 3, 5- triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl -7,7,9,9-tetramethyl-1,3, 8-triazaspiro [4.5] decan-2,4-dione, 3 -dodecyl 1- (2,2,6, 6 -t emethyl-4-piperidyl) pyrrolidin-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidin-2, 5-dione. 6. Oxalamides, for example 4,4'-dioctyloxoxanilide, 2,2'-diethoxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5, 5 '-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2- ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, mixtures of o- and p-methoxy disubstituted oxanilides and mixtures of disubstituted o- and p-ethoxy oxanilides. 7. 2- (2-Hydroxyphenyl) -1,3,5-triazines, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2- hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyl-oxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy) - 4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethyl-phenyl) ) -1,3, 5- triazine, 2 - [2-hydroxy-4- (2-hydroxy-3-butyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3, 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4 - (dodecyl / tridecyloxy-2-hydroxypropyloxy) -2-hydroxy-phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine. 8. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilaurylphosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl penta-erythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2) , 6-di-tert-butyl-me-1-phenyl) -pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2, 4, 6-tris) (tert-butyl-phenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butyl phenyl) -, 4'-biphenylene diphosphonite, 6-isooctyloxy-2, 4,8, 10-tetraether -butyl-12H-dibenz - [d, g] -1,3, 2-dioxaphosphozin, 6-fluoro-2, 4,8, 10 -tetra-tert-butyl-12 -methyl-dibenz- [d, g] -1,3,2-dioxaphosphozin, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) - and the phosphite.

Illustrative examples of additional additives are: Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood sawdust and flours or "fibers of other natural products, synthetic fibers Other additives, for example plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, leveling assistants, optical brighteners, flameproof agents, Antistatic Agents and Blowing Agents In addition to the additives indicated above, it is also possible that additional coinitiators are present.In general, these are dyes that improve the total quantum yield for example by energy transfer or electron transfer. which can be added as coinitiators are triarylmethanes, for example bad green aquita, indolines, thiazines, for example methylene blue, xanthones, thioxanthones, oxazines, acridines or phenazines, for example saf anine and rhodamines of the formula wherein R is alkyl or halo; and R 'is hydrogen, an alkyl or aryl radical, for example Rhodamine B, Rhodamine 6G or Violamine R, and also Sulforhodamine B or Sulforhoda ine G. Preference is given to thioxanthones, oxazine, acridines, phenazines and rhodamines. Bleaching combinations with borates are also convenient in this connection, as described among others in US 4772530, GB 2307474, GB 2307473, GB 2307472 and EP 775706. In addition to the catalyzable binders per base (curable) described above, component B), the composition can also include other binders equally. It is possible to use, for example, additional olefinically unsaturated compounds. The unsaturated compounds may include one or more olefinic double bonds. They can be of low molecular mass (monomeric) or high molecular mass (oligomeric). Examples of monomers having a double bond are alkyl acrylates or hydroxyalkyl acrylates or alkyl methacrylates or hydroxyalkyl methacrylates, such as ethyl, butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate or ethyl methacrylates. Silicone acrylates are also of interest. Additional examples are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamides, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl- and halo-styrenes, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride. . Examples of monomers having two or more double bonds are the diacrylates of ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol or bisphenal A, 4,4'-bis (2-acryloyl-oxyethoxy) diphenylpropane, trimethylolpropane triacrylate, pentaerythiol tritol triacrylate or pentaerythritol tetraacrylate, vinyl acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, triaryl phosphate, triaryl isocyanurate or tris (2-acryloylethyl) isocyanurate. Examples of polyunsaturated compounds of higher molecular mass (oligomers) are acrylated epoxy resins, acrylated polyesters or polyesters containing vinyl ether groups or epoxy groups, polyurethanes and polyethers. Additional examples of unsaturated oligomers are unsaturated polyester resins which are primarily prepared from maleic acid, phthalic acid and one or more diols and have molecular weights of about 500 to 3000. In addition, it is also possible to employ vinyl ether monomers and oligomers and also oligomers terminated with maleate with polyester, polyurethane, polyether, polyvinyl ether and epoxy main chains. In particular, combinations of functional vinyl ether-carrying oligomers and polymers are as described in WO 90/01512 and are very convenient. Copolymers of vinyl ether and monomers functionalized with maleic acid are also convenient. Unsaturated oligomers of this type can also be referred to as prepolymers. Particularly suitable examples are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides and polymers having ethylenically unsaturated groups in the chain or in side or side groups, such as polyesters, polyamides and polyurethanes and their copolymers, unsaturated, alkyd resins, copolymers of butadiene and polybutadiene, copolymers of isoprene and polyisoprene, copolymers and polymers having (meth) acrylic groups in secondary chains and mixtures of one or more of these polymers. If in addition, these monomers, oligomers / polymers curable by free radicals are used, then it is judicious to add an additional photoinitiator that dissociates into radicals. These photoinitiators are known and produced industrially. Examples are benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, for example a-hydroxycycloalkyl phenyl ketones, dialkoxyacetophenones, a-hydroxy- or a-aminoacetophenones, 4-aroyl-l, 3-dioxolanes, benzoyl alkyl ethers and benzyl ketals, monoacyl phosphine oxides, bisacylphosphine oxides, compounds. of ferrocenium or titanocenes. Examples are given in EP-A-284 561.

Polymer systems of this type, wherein curing / entanglement is carried out by different mechanisms are also referred to as hybrid systems. It is also possible to add non-reactive binders to novel compositions, which is particularly judicious if the. Photopolymerizable compounds are liquids or viscous substances. The amount of the non-reactive binder for example may be 5-95%, preferably 10-90% and in particular 40-90% by weight based on the total solids content. The selection of the non-reactive binder is made according to the field of use and with the properties required for this use, such as the possibility for development in aqueous and organic solvent systems, substrates adhesion and sensitivity to oxygen.

Examples of suitable binders are polymers having a molecular weight of about 5,000-2,000,000, preferably 10,000-1,000,000. Examples are homo- and copolymeric acrylates and methacrylates, for example copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly (alkyl methacrylates), poly (alkyl acrylates); cellulose esters and ethers such as cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose; polyvinyl butyral, polyvinylforraal, cyclized rubber, polyethers such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran; polystyrene, polycarbonate, polyurethane, chlorinated polyolefins, polyvinyl chloride, copolymers of vinyl chloride / vinylidene chloride, copolymers of vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, copolymer (ethylene vinyl acetate), polymers such as polycaprolactam and poly (hexamethylene adipamide) and polyesters such as poly (ethylene glycol texephthalate) and poly (hexamethylene glycol succinate). Additionally, the invention provides a method for carrying out base catalyzed reactions comprising subjecting A) A) to at least one compound having a structural unit of the formula (I) (I), wherein Rx is an aromatic or heteroaxomatic radical able to absorbex light in the range of wavelengths from 200 to 650 nm and in doing so achieves rupture of the adjacent carbon-nitrogen bond; and B) at least one organic compound that is capable of a base catalyzed reaction, which is a composition as described above, to irradiation with light of wavelength from 200 nm to 650 nm. Component A) is preferably an organic compound as described above of formula (III), including preferred meanings indicated. Examples and preferred meanings for reactions catalyzed by base, have already been given previously. In some cases, it may be advantageous to carry out heating during or after exposure to light. In this way it is possible in many cases to accelerate the entanglement reaction.

In addition, the method described above paxa pxoducir coatings, model compositions or photo-structured layers is according to the invention. The light sensitivity of the novel compositions generally extends from about 200 nm through the UV region and into the infrared region (about 20,000 nm, in particular 1200 nm) and therefore extends over a very wide range . Convenient radiation comprises for example sunlight or light from artificial sources. Therefore, a large number of very different types of light sources can be used. Both point sources and flat radiators (mats or lamp benches) are convenient. Examples are carbon arc lamps, xenon arc lamps, mercury lamps of medium pressure, high pressure and low pressure, if desired adulterated with metal halides (halogen-metal lamps) metal vapor lamps excited by microwaves , excimer lamps, superactinic fluorescent tubes, fluorescent lamps, incandescent argon lamps, electronic flashing lamps, high intensity lamps or photographic projectors, electron beams and x-rays X, which are produced by synxotxones or laser plasma. The distance between the lamp and the substrate according to the invention to be exposed may vary depending on the application and the type and / or lamp energy, for example between 2 and 150 cm. Laser light sources, for example excimer lasers, are also particularly suitable. Laser in the visible region or in the IR region can also be used. The high sensitivity of the novel materials and the possibility of adapting a coloxant as coiniciadox to the laser line is very advantageous here. By this method it is possible to produce printed circuits in the electronics industry, lithographic offset printing plates or relief printing plates and also photographic recording or recording materials. The novel compositions can be used for various purposes, for example as printing inks, as transparent coatings, as white paints, for example for wood or metal, as coating materials, among others for paper, wood, metal or plastic, as coatings in dust, such as coatings curable with daylight, to mark buildings and roads, for photographic reproduction processes, for holographic recording materials, for image recording processes or for the production of printing plates that can be revealed using organic solvents or aqueous alkaline media, for the production of masks for stencil printing, as dental filling materials, as adhesives including pressure sensitive adhesives, as laminating resins, as mordant protective layers or permanent protective layers and as welding masks for electronic circuits, for the production of articles Three-dimensional particles by mass curing (UV curing in transparent molds) or by the stereolithography process, as described, for example, in US Pat. No. 4,575,330, for the preparation of composite materials (for example styrenic esters which may contain glass fibers and / or other fibers and other auxiliaries (and other thick layer compositions, for the coating or encapsulation of electronic components, or as coatings for optical fibers) In surface coatings, it is common to use mixtures of a premer with unsaturated monomers that also contain a monosaturated monomer.The premer here is primarily responsible for the properties of the coating film and varying it allows the worker with dexterity in the specialty it influences the properties of the cured film.The unsaturated monomer functions as an interlayer which makes the coating film insoluble.The monounsaturated monomer functions as a reactive diluent by which the viscosity is reduced without need for using a solvent.

Unsaturated polyester resins are primarily used in two-component systems in conjunction with a mono-unsaturated monomer, preferably styrene. For protective photocaps, specific one-component systems are frequently used, for example polymaleimides, polyhalcondes or polyimides as described in DE-A-2 308 830. The novel photocurable compositions are suitable, for example, as coating materials for substrates of all types, examples are wood, textiles, paper, ceramics, glass, plastics such as polyesters, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films and also metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO ,, in which it is the intention to apply a protective coating or by exposure in the manner of an image, of an image. The substrates can be coated by applying a liquid composition, a solution or suspension to the substrate. The selection of the solvent and the concentration depend predominantly on the type of composition and the coating process. The solvent must be inert; in other words, it should not undergo any chemical reaction with the components and should be able to be removed again after the coating operation in the drying process. Examples of suitable solvents are ketones, ethers and esters, such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, l-methoxy-2-propanol, , 2-dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl 3-ethoxypropionate. Using known coating processes, the solution is uniformly applied to a substrate, for example by spin coating, dip coating, spatula coating, curtain coating, brushing or brushing, spraying especially by electrostatic spraying and reverse roll coating, and by electrophoretic deposition. It is also possible to apply the photosensitive layer to a temporary flexible support and then coat the final substrate for example a circuit board with copper coating by layer transfer by lamination. The amount applied (layer thickness) and the nature of the substrate (layer support) are functions of the desired field of application. The range of layer thicknesses generally comprises values from about 0.1 μm to more than 100 μm. The novel radiation-sensitive compositions can also be subjected to image exposure.

In this case, they are used as negative protective layers. They are suitable for electronic components (electroplating protective coatings, etching protective coatings and welding protective coatings), for the production of printing plates, such as offset printing plates, flexographic and relief printing plates or stencil printing plates, for the production of marking seals and can be used for etching molded articles or as protective micro-layers in the production of integrated circuits. There is a wide range of variation correspondingly in the possible layer supports and in the processing conditions of the coated substrates. The term "image-like" exposure refers to both exposure through a photomask containing a predetermined pattern, for example a slide, exposure by a laser beam moving under computer control, for example on the surface of the coated substrate and in this way generates an image and irradiation with electron beams controlled by computer. Following the exposure as an image of the material and before development, it may be advantageous to carry out a brief heat treatment, where only the exposed parts are thermally cured. The temperatures employed in general are 50-150 ° C and preferably 80-130 ° C; The duration of the heat treatment in general is between 0.25 and 10 minutes. An additional field of use for light curing is that of metal coatings, for example the surface coating of metal panels and tubes, cans or bottle caps and curing in polymer coatings, for example of floor or wall coverings, with PVC base. Examples of the curing of paper coatings are the colorless varnishing of labels, recording linings or book covers. Also of interest is the use of novel compounds for curing shaped articles made from composite compositions. The composite composition consists of a self-supporting matrix material, for example a fiberglass cloth, or also, for example, vegetable fibers [see K.-P. Miec, T. Reussmann in Kunststoffe 85 (1995), 366-370], which is impregnated with the light-cured formulation. The molded articles made from materials produced with the novel compounds reach a high level of mechanical stability and strength. The compounds of the invention can also be used as light curing agents in molding, impregnation and coating compositions, such as described in EP-A-7086. These compositions, for example, are thin-coating resins, which are subjected to strict requirements regarding their cure activity and resistance to yellowing and to fiber-reinforced molded articles such as light diffusion panels which are planar or which have longitudinal or transverse corrugation. The invention further provides the use of a compound as described above comprising a structural linkage of formula (I), as a photoinitiator for photochemically induced, base catalyzed addition or substitution reactions. Examples of preferred compounds comprising a structural element of the formula (I), as well as substrates suitable for base catalyzed substitution or addition reactions, were established above. The invention further provides a coated substrate that has been covered on at least one surface with a composition as described above and a method for the photographic production of relief images, wherein a coated substrate is subjected to image exposure and then the unexposed areas are removed with a solvent. Of particular interest in this context is the aforementioned exposure by means of a laser beam. The invention further provides an interlaced or polymerized composition as described above. The following examples illustrate the invention. Examples A: Preparation of the photoinitiators General Method of Preparation a) A solution of the corresponding a-bromoketone in toluene is added with stirring to a solution of 1,5-diazabicyclo [4.3.0] nonane in toluene and further stirred during the night at room temperature. The reaction mixture is filtered, washed with demineralised water and dried over MgSO4. Subsequently, it is dried under vacuum to give yields of approximately 85% of the corresponding corresponding a-amino ketone. B) Methyltriphenylphosphonium bromide and sodium amide are stirred in dichloromethane for 15 minutes, then a solution of the a-aminoaceate prepared according to a) is added in dichloromethane, and the mixture is stirred at room temperature for 18 hours. The solution is filtered and the filtrate is concentrated in vacuo. The crude yield of a-amino ketone is 65-85%.

The molar extinction coefficients e in the examples have the dimension 1 / mol cm. Example Al Rx = biphenylyl, R2 = R3 = H, R4 / R6 = - (CH2) R3-, R5 / R7 Analysis calculated for C 22 H 26 N 2: C 82.97; H 8.23; N 8.80.

Found: C 82.83; H 8.26; N 8.59. U.V. (CHCl3) max. at 275 nm (e 21600). GO. (KBr) 1625 and 1600 cm "1 (C = C) .H NMR (CDC13); 7.68-7.28 (9H, m, ArH), 5.51 (1H, s, = CH), . 29 (1H, 5, = CH), 3.83 (1H, d, J 13.3 Hz, NCH2C (CH2) Ph), 3. 07 (3H, m, NCH2), 2.89 (1H, d, J 13.3 Hz, NCH2C (CH2) Ph), 2. 38-1.12 (lOH, m, CH2). 13 C NMR (CDCl 3): 144.14, 141.02, 140.27, 139.31, 128.82, 127. 25, 127.08, 126.99, 126.92, 115.43, 85.08, 58.92, 52. 33, 51.92, 51.19, 29.52, 24.75 and 19.55. m / z (El) 318 (M +) Example A2 Rx = 2-naphthyl, R2 = R3 = H, R4 / R6 = - (CH2) 3-, R5 / R7 = - (CH2) R3-, i / = ía = H Analysis calculated for C20H24N2: C 82.15; H 8.27; N 9.58.

Found: C 82.25; H 8.25; N 9.24. U.V. (CHC13) max. at 247 nm (e 35600) and 287 nm (e 8600). GO. (KBr) 1625 and 1595 cm "1 (C = C) .XMR (CDC13): 7.95 (1H, S, ArH), 7.85-7.65 (4H, m, ArH), 7.45-7.35 (2H, m, ArH ), 5.58 (1H, s, = CH), 5.39 (1H, s, = CH), 3.88 (1H, d, J 13.6Hz, NCH2C (CH2) Ph), 3.07 (3H, m, NCH2), 2.97 (1H, d, J 13.7Hz, NCH2C (CH2) Ph), 2.44-1.45 (lOH, m, CH2). 13 C NMR (CDCl 3): 144.57, 137.84, 133.41, 132.97, 128.37, 127.68, 127.53, 125.96, 125.78, 125.15, 124.94, 115.79, 84. 94, 58.65, 52.21, 52.09, 51.12, 29.49, 24.58 and 19.58. m / z (El) 292 (M +). Example A3 Rx = 4-diethylaminophenyl, R2 = R3 = H, R4 / R6 = - (CH2) R3-, R5 / R- U.V. (CHCI3) max. at 245 nm (e 3700) and 305 nm (e 16100). l.R.

(KBr) 1610 cm "1 and 1520 cm" 1 (C = C). X NMR (CDCl 3): 7.48 (2H, d, ArH), 6.58 (2H, d, ArH), 5.32 (1H, s, = CH), 5.05 (1H, s, = CH), 3.74 (1H, d, J 13.1 Hz, NCH2C (CH2) Ph), 3.32 (4H, q, J 7.1 Hz, NCH2CH3), 3.06 (3H, M, NCH2), 2.80 (1H, d, J 13.1 Hz, NCH2C (CH2) Ph), 2.36 1.23 (10H, m, CH2), and 1.13 (6H, t, J 7.1 Hz, CH3), 13C NMR (CDCI3): 147.21, 143.63, 131.43, 127.36, 111.34, 110.07, 84.21, 59.02, 52.30, 51.81, 51.24, 44.40, 29.42, 24.75, 19.53 and 12.71. m / z (El) 313 (M +). Example A4 Rx = 4-thiomethylphenyl, R2 = R3 = H, R4 / R6 = - (CH2) R3-, R5 / R7 = - (CH2) R3-, R17 = R18 = H U.V. (CHDC13) max. at 280 nm (e 13800). GO. (KBr) 1670, 1625 and 1595 cm "1 (C = C) XH NMR (CDCI3): 7.48 (2H, d, ArH), 7.16 (2H, d, ArH), 5.41 (1H, s, = CH) , 5.21 (1H, s, = CH), 3.74 (1H, d, J 13.2Hz, NCH2C (CH2) Ph), 3.05 (3H, m, NCH2), 2.83 (1H, d, J 13.2Hz, NCH2C (CH2 ) Ph), 2.44 (3H, s, SCH3), 2.30-1.4 (lOH, m, CH2). 13 C NMR (CDCl 3): 143.83, 137.46, 137.16, 126.89, 126.49, 114.93, 84.99, 58.85, 52.25, 51.78, 51.12, 29.42, 24.67, 19.48 and 15.97. m / z (El) 288 (M). Example A5 Rx = phenyl, R2 = H, R3 CH, R4 / R6 - (CH2) R3 R5 / R7 = R17 = R18 = H Analysis calculated for C? 7H24N2: C 79.64; H 9.43; N 10.93. Found: C 79.64; H 9.46; N 10.75. U.V. (CHCI3) max. at 244 nm (e 6700). GO. (KBr) 1630, 1600 and 1575 cm "1 (C = C).? NMR (CDCI3): 7.50-7.17 (5H, m, ArH), 5.35 (0.75H, s, = CH), 5.24 (0.25H, s, = CH), 5.15 (0.75H, s, = CH), 5.10 (0.25H, S, = CH), 4.06 (1H, q, J 6.8Hz, NCHCH3, 2.94 (3H, m, NCH2), 2.63 (1H, m, NCH2), 2.2-1.2 (9H, m, CH2), 1.36 (0.75H, d, J 7.0Hz, CH3) and 1.13 (2.25H, d, J 6.8Hz, CH3) .13C NMR ( CDCI3): 150.38, 142.89, 128.16, 127.04, 126.93, 114. 95 (secondary diasteromer), 114.48 (major diastereomer), 82.18 (secondary diasteromer), 82.03 (major diastereomer), 56.37, 52.24f, 51.60, 43.27, 28.99 (secondary diasteromer), 28.73 (major diastereomer), 25.62 (major diastereomer) , 25.14 (main diaesterómero), 19.36 and 9.35. m / z (DCI) 256 (M +).-Example A6 Rx = 4-biphenyl, R2 = H, R3 = CH3, R4 / R6 = - (CH2) R3-, R5 / R7 = - (CH2) R3-, R17 = R18 = H.

U.V. (CHC13) max. at 266 nm (e 19200). GO. (KBr) 1625, 1600, 1580 cm "1 (C = C).? NMR (CDCI3): 7.49-7.14 (9h, ArH), 5.29 (0.8H, s, = CH), . 18 (0.2H, S, = CH), 5.05 (0.8H, s = CH), 5.00 (0.2H, s = CH), 4. 00 (1H, q, J 6.5Hz, NCHCH3), 2.91 (2H, m, NCH2), 2.75 (1H, m, NCH2), 2.52 (1H, m, NCH), 2.1-1.2 (9H,, CH2) and 1.04 (3H, d, J 6.8HzM CH3). 13C NMR (CDC13): 150.00, 141.80, 141.18, 139.88, 128.83, 128.74, 127.46, 127.33, 127.11, 127.02, 126.90, 126.85, 114..51, 82.18, 57.33 (secondary diaesteromer), 56.30 (main diaesteromer), 52.28 (main diaesteromer), 51.96 (secondary diaesteromer), 51.63 (main diaesteromer), 51.34 (secondary diasteromer), 46.18 (secondary diasteromer), 43.27 (main diaesteromer), 29.10 (secondary diasteromer), 28.76 (main diastereomer), 25.64 (secondary diaesteromer), 25.19 (main diastereomer), 19.36 (main diaesteromer), 18.74 (secondary diasteromer), 15.35 (secondary diasteromer), 9.27 (main diaesterómero). m / z (El) 332 (M +). Example A7 Rx = 1-naphthyl, R2 = H, R3 = CH3, R4 / R6 = - (CH2) R3-, R5 / R7 = - (CH2) R3-, R17 = R? 8 = H.

U.V. (CHC13) max. at 271 nm (e 26900) and 280 nm (6000). GO. (KBr) 1620, 1590, 1570 cm "1 (C = C) .XMR (CDC13): 7.77-7.52 (5H, m ArH), 7.42-7.30 (2H, m ArH), 5.54 (0.75H, s, = CH), 5.40 (0.25H, s, = CH), 5.31 (0.75H, S, = CH), 5.29 (0.25H, S, = CH), 4.14 (IH, q, J 6.8Hz, NCHCH3), 2.87 (3H, m, NCH2), 2.62 (1H, m, NCH), 2.1-1.0 (12H, m, CH2 and CH3). 13C NMR (CDCI3): 150.84, 140.43, 133.48, 132.80, 128.11, 127.75, 127.65 , 127.54, 127.49, 126.09, 125.80, 125.62, 125.60, 114.86, 82.18 (secondary diaesteromer), 81.95 (major diaesteromer), 57.22 (secondary diasteromer), 56.33 (main diaesteromer), 52.08 (main diaesteromer), 51.89 (secondary diaesteromer), 51.46 (main diaesteromer), 51.26 (secondary diaesteromer), 46.00 (secondary diaesteromer), 43.41 (main diaesteromer), 29.02 (secondary diaesteromer), 28.78 (major diaesteromer), 25.60 (secondary diasteromer), 25.00 (major diastereomer), 19.39 (main diaesteromer), 19. 07 (secondary diaesteromer), 9.43. m / z (El) 306 (M +). Example A8 Rx = 2-naphthyl, R2 = H, R3 = CH3, R4 / R6 = - (CH2) R3-, R5 / R7 = - (CH) R3 -, R17 = R18 = H U.V. (CHC13) max. to 245 (e 5660). GO. (KBr) 1625, 1600, 1570 cm "1 (C = C) X NMR (CDCI3): 7.83-7.72 (4H, m ArH), 7.60 (1H, m ArH), 7.47-7.24 (2H, m ArH) , 5.46 (0.75H, s, = CH), 5.37 (0.25H, s, = CH), 5.25 (075H, s, = CH), 5.20 (0.25H, s, = CH), 4.20 (1H, q, J 6.8Hz, NCHCH3), 3.01-2.65 (4H, m), 2.18-1.43 (9H, m) and 1.18 (3H, d, J6.8Hz, CH3) .13C NMR (CDC13): 150.81, 140.45, 133.49, 132.81, 128.12, 127.53, 125.77, 125.62, 125.48, 82.18 (secondary diasteromer), 81.95 (secondary diasteromer), 56.32, 52.07 (main diaesteromer), 51.88 (secondary diasteromer), 51.45 (main diaesteromer), 51.28 (secondary diaesteromer), 43.40, 29.08 (secondary diaesteromer), 28.78 (main diaesteromer), 25.41 (secondary diaesteromer), 25.00 (main diasteromer), 19.39, 9.45. m / z (El) 306 (M +). Example A9 Rx = 2-thiantrenyl, R2 = H, R3 = CH3, R4 / R6 = - (CH2) R3-, R5 / R7 = - (CH2) R3-, R17 = R18 = H.

U.V. (CHCI3) max. at 262 nm (e 29800). GO. (KBr) 1625, 1580 cm "1 (C = C).: H NMR (CDC13): 7.47-7.17 (7H, m ArH), 5.32 (0.9H, s, = CH), 5.24 (0.1 H, S, = CH), 5.15 (0.9H, s, = CH), 5.11 (0.1H, s, = CH), 4.00 (1H, q, J 6.7Hz, NCHCH3), 3.03-2.60 (4H, m), 2.2- 1.16 (9H, m) and 1.12 (3H, d, J 6.7Hz, CH3). 13 C NMR (CDCl 3): 149.46, 142.80, 135.82, 135.75, 135.07, 133.80, 128.73, 128.69, 128.37, 127.59, 127.54, 127.10, 126.43, 115.63 (secondary diastereomer), 115.10 (major diaesteróraero), 82.00 (secondary diaesteromer), 81.80 (major diaesteromer), 57.37 (secondary diaesteromer), 56.25 (major diastereomer), 52.12 (major diastereomer), 51.83 (secondary diasteromer), 51.40 (major diastereomer), 51.21 (secondary diastereomer), 46.65 (secondary diasteromer), 43.26 ( main diaesteromer), 29.75 (secondary diaesteromer), 28.81 (major diastereomer), 25.57 (secondary diasteromer), 25.03 (main diaesteromer), 19.38 (main diastereomer), 18.27 (secondary diasteromer), 14.16 (secondary diasteromer), 9.21 (main diaesteromer ). m / z (El) 394 (M +). Example A10 Rx = 2-thioxanthyl, R2 = H, R3 = CH3, R4 / R6 = - (CH2) R3-, R5 / R7 = - (CH2) R3-, R17 = R18 = H.

U.V. (CHC13) max. at 391 nm (e 4000) and 266 nm (e 28700). GO. (KBr) 1640, 1592 cm "1 (C = C). XH NMR (DMSO-d6): 8.49 (1H, d, ArH), 8.47 (1H, d, ArH), 7.89 (1H, dd, ArH), 7.85 (1H, d, ArH), 7.79 (1H, d, ArH), 7.77 (IH, t, ArH), 7.59 (1H, t, ArH), 5.51 (0.9H, s, = CH), 5.45 (0.1 H, s, = CH), 5.26 (0.9H, s, = CH), 5.18 (0.1H, s, = CH), 4.19 (1H, q, J 5Hz, NCHCH3), 2.85-2.80 (4H, m) , 2.10-1.19 (9H, m) and 1.16 (3H, d, J 7Hz, CH3) .13C NMR (CDCI3): 178.8, 149.2, 140.6, 136.5, 135.75, 134.9, 132.9, 131.7, 129.1, 128.3, 128.0, 126.8, 126.6, 126.1, 115.3, 81.1, 55.1, 51.5, 50.5, 42.5, 28.0, 24.5, 19.0, 8.5, m / z (El) 390 (M +). Example All Rx = 3,4-trimethoxyphenyl, R2 = H , R3 = CH3, R4 / R6 = - (CH2) R3-, R5 / R7 = ~ (CH2) R3-, Ru = R18 = H.

Analysis calculated for C20H30N203: C 69.33; H 8.73; N 8.09. Found: C 69.14; H 8.71; N 8.06. U.V. (CHCI3) max. at 319 nm (e 1000) and 250 nm (e 7100). GO. (KBr) 1681, 1578 cm "1 (C = C).

JH NMR (CDCl 3): 6.65 (1.6H, s, ArH), 6.51 (0.4H, s, ArH), 5.29 (0.8H, s, = CH), 5.24 (0.2H, S, = CH), 5.10 ( 0.8H, S, = CH), 5.06 (0.2H, s, = CH), 4.04 (1H, q, J 6.8Hz, NCHCH3), 3.81 (9H, s, OCH3), 2.98-2.79 (3H, m) , 2.62 (1H, m), 2.18-1.17 (9H, m) and 1.12 (3H, d, J 6.7Hz, CH3). 13 C NMR (CDCl 3): 152.8, 150.6, 138.7, 114.2, 104.3, 81.9, 60.7, 56.4, 56.2, 52.1, 51.5, 43.2, 28.8, 25.1, 19.4, 9.3. m / z (El) 346 (M +). Example A12 Rx = 4-thiomethylphenyl, R2 = H, R3 = CH3, R4 / R5 = - (CH2) R3-, R5 / R7 = _ (CH2) R3-, R17 = R18 = H.

Analysis calculated for C? 8H26N28: C 71.48; H 8.66; N 9.26; S 10.60. Found: C 71.48; H 8.60; N 8.44; S 10.47. U.V. (CHCI3) max. at 275 nm (e 14100). GO. (KBr) 1620, 1593 cm "1 (C = C) .XMR (CDC13): 7.43-7.14 (4H, m, ArH), 5.34 (0.75H, s, = CH), 5.22 (0.25H, s, = CH), 5.11 (075H, S, = CH), 5.06 (0.25H, s, = CH), 4.05 (1H, q, J 6.7Hz, NCHCH3), 3.06-2: 59 (4H, m), 2.44 (3H, s, SCH3), 2.17-1.34 (9H, m) and 1.12 (3H, d, J 6.7Hz, CH3) .XH NMR (CDC13): 149.7, 139.7, 136.8, 127.5, 127.4, 126.6, 126.4, 114.1, 82.0, 56.2, 52.2, 51.6, 51.3, 43.2, 28.7, 25.2, 19.3, 9.2, m / z (El) 302 (M +). Example Al 3 Rx = 2 -fluorenyl, R2 = H, R3 = CH3, R4 / R6 = - (CH2) R3-, R5 / R7 = - (CH2) R3 -, R17 = R18 = H.

U.V. (CHC13) max. at 281 nm (e 19500). GO. (KBr) 1623, 1611 cm "1 (C = C) .XH NMR (CDCI3): 7.78-7.23 (7H, m, ArH), 5.42 (0.75H, s, = CH), 5.32 (0.25H, s, = CH) 5.19 (075H, s, = CH), 5.14 (0.25H, s, = CH), 4.14 (1H, q, J 6.5Hz, NCHCH3), 3.88 (2H, m, 'C9 fluorenil), 3.16 -2.87 (3H, m), 2.68 (1H, q, J 5.6Hz), 2. 20-1.24 (9H, m) and 1.17 (3H, d, J 6.7Hz, CH3). 13 C NMR (CDCl 3): 150.8, 143.5, 143.1, 141.7, 140.7, 126.7, 126.4, 125.8, 1, 125.0, 123.5, 119.8, 119.5, 114.8 (secondary diaesteromer), 114.2 (major diastereomer), 82.2 (secondary diaesteromer) 82.0 (major diaesteromer), 57.3 (secondary diasteromer), 56.5 (major diastereomer), 52.1 (major diastereomer), 52.0 (secondary diastereomer), 51.5 (secondary diaesteromer), 51.3 (secondary diasteromer), 45.7 (secondary diasteromer), 43.4 (main diaesteromer), 37.0 (C9 fluorenyl), 29.0 (secondary diaesteromer), 28.8 (major diaesteromer), 25.7 (secondary diasteromer7), 25.1 (major diastereomer), 19.4, 9.5. m / z (El) - 344 (M +). Example To Rx = phenyl, R2 = H, R3 = CH3, R4 / R6 = - (CH2) R3-, R5 / R7 = - Orí2) R-3 - 1 -R-17 - -H. , -R-18 ~ C.H3 : H NMR (CDC13): 7.31-7.10 (5H, m ArH), 5.70-5.50 (1H, m, --CH), 3.80 (1H, m, NCHCH3), 2.94 (3H, m, NCH2), 2.61 ( 1H, m, NCH), 2.1-1.0 (15H, m, CH2 and CH3). Examples of use B: Base catalysis with compounds monome icos Examples B1-B4 Addition of Michael initiated by UV. 7. Four . 10 ~ 5 moles of photoinitiator (latent amidine base) are dissolved in a mixture of dimethyl malonate and n-butyl acrylate (1: 1, 200 mg corresponding to 7.4.10"" moles) in a quartz vessel. The mixture is irradiated with a mercury lamp with high pressure (200 W) from a distance of 30 cm. The conversion is verified as a function of time. The results are set forth in Table 1.

Table 1 Examples of use C: Base catalysis with compounds oligomer / polymer Example Cl Preparation of a urethane acrylate based on isophorone diisocyanate and 4-hydroxybutyl acrylate. The reaction is carried out under a nitrogen atmosphere and all commercial chemicals used are used without further purification. 1566.8 g (13.78 moles of NCO) of isophorone diisocyanate, 2.3 g of dibutyltin dilaurate, 2.3 g of 2,5-di-tert-butyl-p-cresol and 802.8 g of butyl acetate are charged to a three-necked flask equipped with condenser and addition device. Dry nitrogen is bubbled through the reaction mixture and the temperature rises slowly to 60 ° C. 1987 g (13.78 moles) of 4-hydroxybutyl acrylate are added, during which the reaction solution is heated slowly to 80 ° C. The temperature is maintained at 80 ° C and the addition device is flooded with butyl acetate (86.6 g). The reaction is verified by titration of the remaining amount of isocyanate, and ends when the isocyanate content is less than 0.2% based on the solids content. The reaction product obtained has the following physical properties: residual 4-hydroxybutyl acrylate: < 0.002% based on solids (HPLC analysis), Color: «Gardner 1, Viscosity: 43 cPa s (20 ° C), Solids content: 79.3% (1 hour at 140 ° C), GPC data (standard polystyrene ): Mn 778, MH 796, d = 1.02. Preparation of a polyester malonate The reaction is carried out under a nitrogen atmosphere and all commercial chemicals were used without further purification. In a reaction vessel with agitator and condenser, 1045 g of 1,5-pentanediol, 1377.4 g of diethyl malonate and 242.1 g of xylene are carefully refluxed. The maximum temperature of the reaction mixture is 196 ° C while the temperature in the condenser head is maintained at 79 ° C. In this way 862 g of ethanol, corresponding to a conversion of 97.7%, are separated by distillation. The xylene is then extracted under vacuum at a temperature of 200 ° C. The resulting polymer has a solids content of 98.6%, a viscosity of 2710 mPa s and an acid number of 0.3 mg KOH / g based on the solids content. Mn is 1838, Mw is 3186, color is 175 on the APHA scale ("Hazen color number" - ISO 6271 of the American Health Association). Curing with UV light (6.4 x 10"5 moles) of the photoinitiator of Example A5 are dissolved in a 1.3: 1 mixture of the urethane acrylate and the polyester malonate (total amount 400 mg) described above.A film with a thickness of 50 μm is stretched on a glass plate and exposed using a high pressure mercury lamp (200 W) at a distance of 30 cm.The polymer film is free of tack after 120 minutes.

Claims (23)

CLAIMS 1. An organic compound having a molecular weight of less than 1000, characterized in that it comprises at least one structural unit of the formula (I)
1. (I), wherein Rx is an aromatic or heteroaromatic radical capable of absorbing light in the wavelength range from 200 to 650 nm and in so doing achieves breakdown of the adjacent carbon-nitrogen bond.
2. 2. An organic compound, wherein the structural unit of the formula (I) comprises compounds of the formula (II) wherein R-x is an aromatic or heteroaromatic radical capable of absorbing light in the wavelength range from 200 to 650 nm and in so doing achieves breakdown of the adjacent carbon-nitrone bond; R2 and R3 independently of each other are hydrogen, alkyl having 1 to 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, alkynyl with 3 to 18 carbon atoms, or phenyl and if R2 is hydrogen or alkyl with 1 to 18 atoms of carbon, R3 is additionally a group -CO-Ri4 wherein R14 is alkyl with 1 to 18 carbon atoms or phenyl; R5 is alkyl with 1 to 18 carbon atoms or NR15R16; R4, R6 / R7_ Rls and R16 independently of each other are hydrogen or alkyl having 1 to 18 carbon atoms or R4 and R6, together they form an alkylene bridge with 2 to 12 carbon atoms or R5 and R7, independently of R4 and R6, together they form an alkylene bridge with 2 to 12 carbon atoms or if R5 is NR15R16 / R16 and R7 together form an alkylene bridge with 2 to 12 carbon atoms; R17 is hydrogen or alkyl with 1 to 18 carbon atoms; R18 is hydrogen, alkyl having 1 to 18 carbon atoms or phenyl substituted with alkyl having 1 to 18 carbon atoms, vinyl, alkenyl with 3 to 18 carbon atoms, alkynyl with 3 to 18 carbon atoms, haloalkyl with 1 to 18 carbon atoms, phenyl, N02, OH, CN, OR? 0, SR10, C (0) R ??, C (O) OR? 2 or halogen; and R10? R1X and R12 are hydrogen or alkyl with 1 to 18 carbon atoms.
3. 3. An organic compound according to claim 1, characterized in that Rx is phenyl, naphthyl, phenanthryl, anthracyl, pyrenyl, 5,6,7,8-tetrahydro-2-naphtol, 5,6,7,8-tetrahydro-l -naphthyl, thienyl, benzo [b] thienyl, naphth [2, 3-b] thienyl, thiarenyl, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenaptyatiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl , indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, terphenyl, stilbenyl , fluorenyl or phenoxazinyl, these radicals are unsubstituted or substituted one or more times by alkyl with 1 to 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, alkynyl with 3 to 18 carbon atoms, haloalkyl, ilo with 1 to 18 carbon atoms, N02, NR8R9, N3, OH, CN, OR ?0, SR10, C (0) R ??, C (0) OR12 or halogen; or Rx is a radical of formulas A or B (B), R8, R9, R10, R1; L and R12 are hydrogen, alkyl having 1 to 18 carbon atoms; R 13 is alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms, alkynyl with 2 to 18 carbon atoms, haloalkyl with 1 to 18 carbon atoms, N 0 2, NR 8 R 9, OH, CN, OR 10, SR 10, C (0) R, C (O) 0R12 or halogen; 'and n is 0 or a number 1, 2 or 3.
4. 4. An organic compound according to claim 2, characterized in that and independently of one another are hydrogen or alkyl having 1 to 6 carbon atoms, in particular alkyl with 1 to 4 carbon atoms. carbon atoms.
5. 5. An organic compound according to claim 2, characterized in that R4 and R6 together form an alkylene bridge with 2 to 6 carbon atoms.
6. 6. An organic compound according to claim 2", characterized in that Rs and R7 form an alkylene bridge with 2 to 6 carbon atoms or if R5 is NR15R16 R16 and R7 together form an alkylene bridge with 2 to 6 carbon atoms.
7. 7. An organic compound of the formula (II) according to claim 2, characterized in that Rx is phenyl or naphthyl, these radicals are unsubstituted or are substituted one or more times by CN, NR8R9, N3, N02, CF3, SR10 or OR10, or Rx is tiantrenyl, fluorenyl or thioxanthyl, or Rx is a radical of formula A n is 0 and the radicals R8, R9 and? 0 are hydrogen or alkyl having 1 to 6 carbon atoms; R2 and R3 are hydrogen or alkyl with 1 to 6 carbon atoms; R4 and R6 together form an alkylene bridge with 2 to 6 carbon atoms; R5 and R7 together form an alkylene bridge with 2 to 6 carbon atoms; R17 is hydrogen; and R18 is hydrogen or alkyl having 1 to 4 carbon atoms.
8. 8. A process for preparing compounds having the structural unit of the formula (I) as described above, comprising in a first step, reacting a compound comprising a structural unit of the formula (III) with a compound comprising a structural unit of formula IV Halogen R1 (IV) , wherein Halogen is F, Cl, Br or I and Rx is as defined in claim 1, and in a second step, carrying out a Wittig reaction using a phosphonium salt, with the reaction product thus obtained.
9. 9. A process for preparing compounds of the formula (II) which comprises reacting a compound of the formula (V) wherein the radicals R 4, R 5, R 6 and R 7 are as defined in claim 2, with a compound of the formula IV) Halogen wherein the radicals R 1 R2 and R3 are as defined in claim 2 and Halogen is F, Cl, Br or 1, and in a second step, conducting a Wittig reaction with the reaction product thus obtained, using a salt phosphonium of the formula VII R? 7R18 CH-P (phenyl) 3 + X "(VII), wherein R17 and R18 are as defined in claim 2, and X is F, Cl, Br, I or tetrafluoroborate. A process for preparing a compound of the formula (VII) wherein the radicals R4, R5, R6 and R7 have the meanings given in claim 2, which include exposing a compound of the formula (II) according to claim 2, to light having a wavelength from 200 nm to 650 nm. 11. A composition characterized in that it comprises A) at least one compound having a structural unit of the formula (I) according to claim 1 and B) at least one organic compound capable of substitution reaction or base catalyzed addition. 12. A composition according to claim 11, characterized in that component B) is an anionically crosslinkable or polymerizable organic material. 13. A composition according to claim 11, characterized in that component B) is one of the following systems: a) acrylate copolymers having alkoxysilane or alkoxysiloxane side groups; b) two-component systems comprising polyacrylates containing hydroxyl groups, polyesters and / or polyethers and aliphatic or aromatic polyisocyanates; c) two-component systems comprising functional polyacrylates and a polyepoxide, wherein the polyacrylate contains carboxyl, anhydride groups; d) two-component systems comprising polyacrylates, polyesters and / or polyethers containing hydroxyl group modified with silicone or modified with fluorine and aliphatic or aromatic polyisocyanates; e) two component systems comprising (poly) ketimines and aliphatic or aromatic polyisocyanates; f) two-component systems comprising (poly) ketimines and unsaturated acrylate resins or acetoacetate or methyl a-acrylamidomethylglycolate resins; h) two-component systems comprising (poly) oxazolidines and polyacrylates containing anhydride groups or unsaturated acrylate resins or polyisocyanates; i) two-component systems comprising epoxy functional polyacrylates and polyacrylates containing amino group; 1) polymers based on allyl glycidyl ether; m) two-component systems comprising a (poly) alcohol and a (poly) isocyanate; n) two-component systems comprising a α, β-ethylenically unsaturated carbonyl compound and a polymer containing activated CH 2 groups. 14. A composition according to claim 11, characterized in that the component B) is an epoxy resin or a mixture of different epoxy resins. 15. A composition according to claim 11, characterized in that it is present in an amount from 0.01 to 10% by weight, based on component B). 16. A composition according to claim 11, characterized in that it additionally comprises thioxanthones, oxazines, acridines, phenazines and rhodamines. 17. A method for implementing base catalyzed reactions, characterized in that it comprises subjecting a composition according to claim 11, to irradiation with light having a wavelength from 200 nm to 650 nm. 18. A method according to claim 17, characterized in that heating is carried out during or after exposure to light. The use of an organic compound according to claim 1, characterized in that it is used as photoinitiator for photochemically induced, base catalyzed substitution or addition reactions, 20. The use of an organic compound according to claim 19, characterized because it is used to produce coatings, molding compositions or photo-structured layers. 21. A coated substrate that has been covered on at least one surface with a composition in accordance with claim 11. 22. A polymerized or entangled composition according to claim 11. 23. A method according to claim 17, for producing coatings, molding compositions or photo-structured layers.