FUNCTIONALISED PHOTOINITIATORS, DERIVATIVES AND MACROMERS THEREFROM AND THEIR USE

Abstract: The present invention relates to alpha -aminoacetophenones functionalised with organic diisocyanates, having general structure (I) which can be used as reactive photoinitiators; to oligomers and polymers to which such functionalised alpha -aminoacetophenones are bonded; to alpha -aminoacetophenones having an unsaturated polymerisable side-chain; to dimeric and trimeric photoinitiators; to the use of such photoinitiators; to materials coated with such photoinitiators; and to the use of functionalised alpha -aminoacetophenones for modifying surfaces. In said structure (I), X is bivalent -O-, -NH-, -S-, lower alkylene or (a); Y is a direct bond or -O-(CH2)n- wherein n is an integer from 1 to 6 and the terminal CH2 group of which is linked to the adjacent X in formula (I); R is H, C1-C12alkyl, C1-C12alkoxy, C1-C12alkylNH- or -NR1AR1B wherein R1A is lower alkyl and R1B is H or lower alkyl; R1 is linear or branched lower alkyl, lower alkenyl or aryl-lower alkyl; R2 independently of R1 has the same definitions as R1 or is aryl, or R1 and R2 together are -(CH2)m- wherein m is an integer from 2 to 6; R3 and R4 are each independently of the other linear or branched lower alkyl that may be substituted by C1-C4alkoxy, or aryl-lower alkyl or lower alkenyl; or R3 and R4 together are -(CH2)z-Y1-(CH2)z- wherein Y1 is a direct bond, -O-, -S- or -NR1B-, and R1B is H or lower alkyl and z is independently of the other an integer from 2 to 4; R5 is linear or branched C3-C18alkylene, unsubstituted or C1-C4alkyl- or C1-C4alkoxy- substituted C6-C10arylene, or unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted C7-C18aralkylene, unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted C13-C24- arylenealkylenearylene, unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted C3-C8-cycloalkylene, unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted C3-C8cycloalkylene-CyH2y- or unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted -CyH2y-(C3-C8-cycloalkylene)-CyH2y-, wherein y is an integer from 1 to 6; and D is an isocyanato group.

Description: Functionalised photoinitiators. derivatives and macromers therefrom and their use The present invention relates to α-aminoacetophenones functionalised with organic diiso- cyanates, which can be used as reactive photoinitiators; to oligomers and polymers to which such functionalised α-aminoacetophenones are bonded; to α-aminoacetophenones having an unsaturated polymensable side-chain; to dimeric and trimeric photoinitiators; to the use of such photoinitiators; to materials coated with such photoinitiators; and to the use of the functionalised α-aminoacetophenones for modifying surfaces. Alpha-aminoacetophenones of the structural type (A) are known, for example, from EP-A-003002 and are described therein as outstanding photoinitiators for radiation-induced polymerisation of ethylenically unsaturated monomeric, oligomeric or polymeric compounds. Considered to be a disadvantage are the low-molecular-weight fragments produced which emerge from a polymer, for example as a result of migration, and thus may impair its performance properties. In order to avoid that disadvantage and other disadvantages of such monomeric photoinitiators, EP-A- 261 941 proposes modifying photoinitiators at the phenyl nucleus in such a way that the photolysis products are securely bonded into the resulting polymer structure. Also mentioned very generally as functional groups for that purpose are isocyanate groups, which are bonded to the phenyl nucleus via a spacer group, for example a linear alkylene group. The preparation of such compounds poses considerable problems of synthesis, however, since, in the reaction of linear diisocyanates with compounds containing hydroxy groups, the formation of diadducts cannot be avoided or even predominates. There is therefore a need for functional photoinitiators that can be produced easily, that can be obtained in high purity and are distinguished by high reactivity and stability to storage, that can be linked to suitable oligomers or polymers to produce highly effective macromeric photoinitiators, that are suitable for modifying surfaces, especially plastics surfaces, by photo-induced graft polymerisation, and that can also be used for biologically tolerable materials, especially in the biomedical sector. It has been found that that objective can be achieved by using, for the introduction of isocyanate groups, diiso- cyanates that comprise isocyanate groups of differing reactivity and reacting them with α-aminoacetophenones that carry in the phenyl nucleus suitable functional groups accord¬ ing to formula (II) to form compounds of formula (I), in which reaction the formation of isomers and other by-products is suppressed by a high regioselectivity. The invention relates to compounds of formula (I) D — R 5 — NH- C - Y - X NR 3 R 4 (I), wherein X is bivalent -O-, -NH-, -S-, lower alkylene or Y is a direct bond or -O-(CH 2 ) n - wherein n is an integer from 1 to 6 and the terminal CH 2 group of which is linked to the adjacent X in formula (I); R is H, Cι-C 12 alkyl, Ci-C^al oxy, -C^alkylNH- or -NR 1A R 1B wherein R 1A is lower alkyl and Rjg is H or lower alkyl; Rj is linear or branched lower alkyl, lower alkenyl or aryl-lower alkyl; R 2 independently of Rj has the same definitions as Rj or is aryl, or Rj and R 2 together are -(CH^ m " wherein m is an integer from 2 to 6; R 3 and R 4 are each independently of the other linear or branched lower alkyl that may be substituted by C 1 -C 4 alkoxy, or aryl-lower alkyl or lower alkenyl; or R 3 and R 4 together are -(CH 2 ) Z -Yι-(CH 2 ) Z - wherein Yi is a direct bond, -O-, -S- or -NR 1B -, and R 1B is H or lower alkyl and z is independently of the other an integer from 2 to 4; R 5 is linear or branched -Cigalkylene, unsubstituted or Cι-C alky_- or Cι-C 4 alkoxy- substituted Cβ-C arylene, or unsubstituted or Cι-C 4 alkyl- or C 1 -C 4 alkoxy-substituted Cy-Cigaralkylene, unsubstituted or Cj-Qalkyl- or C 1 -C 4 alkoxy-substituted C 13 -C 24 - arylenealkylenearylene, unsubstituted or Cι-C 4 alkyl- or C 1 -C alkoxy-substituted C 3 -Cg- cycloalkylene, unsubstituted or C r C 4 alkyl- or Ci-Qalkoxy-substituted C 3 -C 8 cycloalkyl- ene-C y H 2y - or unsubstituted or Cι-C 4 alkyl- or Cι-C 4 alkoxy-substituted -C y H 2 "(C 3 -C 8 - cycloalkylene)-C y H 2y -, wherein y is an integer from 1 to 6; and D is an isocyanato group. One preferred definition of X is -O-, -NH- or -S-. Another preferred definition of X is lower alkylene. More preferably, X is -O- or -S- and especially -O-. In a preferred definition of Y, the index n is 1 to 5, more preferably 2 to 4, and most preferably 2 or 3, so that Y is, for example, ethyleneoxy or propyleneoxy. In another preferred definition, Y is a direct bond, X then preferably containing at least one hetero atom. The group R contains as alkyl, alkoxy, alkylNH- or -NR 1A R 1B preferably from 1 to 6 and especially from 1 to 4 carbon atoms. Some examples are methyl, ethyl, n- or iso-propyl, n-, iso- or tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, methoxy, ethoxy, propoxy, butoxy, N,N-dimethylamino and N-methylamino. Most preferably, R is H. A preferred definition of -NRj A R 1B is N,N-dimethylamino, N-methylamino, N-methyl-N-ethylamino, N-ethylamino, N,N-diethylamino, N-isopropylamino or N,N-diisopropylamino. Rj is preferably allyl, benzyl or linear Q-Qalkyl, for example methyl or ethyl. R 2 has preferably the same definitions as Rj and is more preferably linear lower alkyl having from 1 to 4 carbon atoms and especially 1 or 2 carbon atoms. R as aryl may be, for example, naphthyl or especially phenyl that is unsubstituted or substituted by lower alkyl or lower alkoxy. When Rj and R 2 together are -(CH- * ),,,-, m is preferably 4 or 5 and especially 5. R 3 is preferably linear lower alkyl having from 1 to 4 carbon atoms, benzyl or allyl, and more preferably methyl or ethyl. 4 is preferably linear lower alkyl having from 1 to 4 carbon atoms and more preferably methyl or ethyl. When R 3 and R together are -(CH 2 Z -Yι-(CH 2 ) Z -, Y \ is preferably a direct bond, -O- or -N(CH 3 )- and most preferably -0-; z is preferably 2 or 3 and especially 2. R 5 is preferably linear or branched C 3 -C 18 alkylene, unsubstituted or Q-Qalkyl- or Ci-Q¬ alkoxy-substituted C 6 -C 10 arylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substi- tuted Cχ 3 -C 24 arylenealkyleneaιylene or unsubstituted or Q-Qalkyl- or Q-Qalkoxy-sub- stituted C 3 -C 8 cycloalkylene, and preferably linear or branched C 3 -C π alkylene, unsubsti- tuted or C j -Qalkyl- or Q-Qalkoxy-substituted C 6 -C 10 arylene, unsubstituted or C j -Q¬ alkyl- or Q-Qalkoxy-substituted Qs-C^arylenealkylenearylene or unsubstituted or C j -Qalkyl- or Q-Qalkoxy-substituted Q-C 8 cycloalkylene. Some examples of linear C 3 -Cj 8 alkylene are 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 1,14-tetradecylene and 1,18-octadecylene. Some examples of branched C 3 -Cj 8 alkylene are 2,2-dimethyl-l,4-butylene, 2,2-dimethyl- 1,5-pentylene, 2,2,3- or 2,2,4-trimethyl-l,5-pentylene, 2,2-dimethyl-l,6-hexylene, 2,2,3- or 2,2,4- or 2,2,5-trimethyl-l,6-hexylene, 2,2-dimethyl-l,7-heptylene, 2,2,3- or 2,2,4- or 2,2,5- or 2,2,6-trimethyl-l,7-hep_ylene, 2,2-dimethyl-l,8-octylene, 2,2,3- or 2,2,4- or 2,2,5- or 2,2,6- or 2,2,7-trimethyl-l,8-octylene. When R5 is arylene, it is preferably naphthylene and especially phenylene. When the arylene is substituted, one substituent is preferably in the ortho-position with respect to an isocyanate group. Examples of substituted arylene are l-methyl-2,4-phenylene, 1,5-di- methyl-2,4-phenylene, l-methoxy-2,4-phenylene and l-methyl-2,7-naphthylene. R5 as aralkylene is preferably naphthylalkylene and especially phenylalkylene. The alkylene group in aralkylene contains preferably from 1 to 12, especially from 1 to 6, and more especially from 1 to 4 carbon atoms. Most preferably, the alkylene group in aralk¬ ylene is methylene or ethylene. Some examples are 1,3- or 1,4-benzylene, naphth-2-yl-7- methylene, 6-methyl-l,3- or -1,4-benzylene, 6-methoxy-l,3- or -1,4-benzylene. When R 5 is cycloalkylene, it is preferably Q- or Q-cycloalkylene that is unsubstituted or substituted by methyl. Some examples are 1,3-cyclobutylene, 1,3-cyclopentylene, 1,3- or 1,4-cyclohexylene, 1,3- or 1,4-cycloheptylene, 1,3- or 1,4- or 1,5-cyclooctylene, 4-methyl- 1 ,3-cyclopentylene, 4-methyl- 1 ,3-cyclohexylene, 4,4-dimethyl- 1 ,3-cyclo- hexylene, 3-methyl- or 3,3-dimethyl-l,4-cyclohexylene, 3,5-dimethyl-l,3-cyclohexylene, 2,4-dimethyl- 1 ,4-cyclohexylene. When R5 is cycloalkylene-CyH 2y -, it is preferably cyclopentylene-C y H 2y - and especially cyclohexylene-CyH 2 y" mat -* s unsubstituted or substituted by preferably from 1 to 3 Q-Q¬ alkyl groups, especially methyl groups. In the group -C y H y -, y is preferably an integer from 1 to 4. More preferably, the group -C y H 2y - is ethylene and especially methylene. Some examples are cyclopent-l-yl-3-methylene, 3-methyl-cyclopent-l-yl-3-methylene, 3,4-dimethyl-cyclopent- l-yl-3-methylene, 3,4,4-trimethyl-cyclopent- l-yl-3-methylene, cyclohex-l-yl-3- or -4-methylene, 3- or 4- or 5-methyl-cyclohex-l-yl-3- or -4-methylene, 3,4- or 3,5-dimethyl-cyclohex-l-yl-3- or -4-methylene, 3,4,5- or 3,4,4- or 3,5,5-trimethyl- cyclohex-l-yl-3- or -4-methylene. When R 5 is -C y H y -cycloalkylene-C y H 2y -, it is preferably -C y H^-cyclopentylene-C y H^- and especially -C y H 2y -cyclohexylene-C y H 2y - that is unsubstituted or substituted by prefer¬ ably from 1 to 3 Q-Qalkyl groups, especially methyl groups. In the group -C y H 2y -, y is preferably an integer from 1 to 4. More preferably, the groups -C y H 2y - are ethylene and especially methylene. Some examples are cyclopentane-l,3-dimethylene, 3-methyl-cyclo- pentane- 1 ,3-dimethylene, 3,4-dimethyl-cyclopentane- 1 ,3-dimethylene, 3,4,4-trimethyl- cyclopentane-l,3-dimethylene, cyclohexane-1,3- or -1,4-dimethylene, 3- or 4- or 5-methyl-cyclohexane-l,3- or -1,4-dimethylene, 3,4- or 3,5-dimethyl-cyclohexane-l,3- or -1,4-dimethylene, or 3,4,5- or 3,4,4- or 3,5,5-trimethyl-cyclohexane-l,3- or -1,4-dimeth- ylene. A preferred sub-group of compounds of formula I comprises those wherein Rj is linear lower alkyl, lower alkenyl or aryl-lower alkyl; R 2 independently of Rj has the same definitions as Rj or is aryl; R 3 and R 4 are each independently of the other linear or branched lower alkyl that may be substituted by Q-Qalkoxy, or aryl-lower alkyl or lower alkenyl; or R 3 and R 4 together are wherein Yj is a direct bond, -0-, -S- or -NRj B -, and R 1B is H or lower alkyl and z is an integer from 2 to 4; and R 5 is linear or branched Q-Qgalkylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy- substituted Q-Qoarylene, or unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted C 7 -Q 8 aralkylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted Q 3 -Q 4 - arylenealkylenearylene, unsubstituted or Q-Qalkyl- or Cj-C 4 alkoxy-substituted Q-Q- cycloalkylene, unsubstituted or Cj-C 4 alkyl- or Cj-C 4 alkoxy-substituted Q-Qcyclo- alkylene-C y H 2y _ OT unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted -C y H 2y -(C 3 -Cgcycloalkylene)-C y H 2y -, wherein y is an integer from 1 to 6. A preferred sub-group of compounds of formula I comprises those wherein X is bivalent -0-, -NH-, -S- or -(CH-^),.-; Y is a direct bond or -0-(CH 2 ) n - wherein n is an integer from 1 to 6 and the terminal CH 2 group of which is linked to the adjacent X in formula (I); R is H, Q-Q 2 alkyl or Q-C 12 alkoxy; R j is linear lower alkyl, lower alkenyl or aryl-lower alkyl; R 2 independently of Rj has the same definitions as Rj or is aryl, or R j and R together are -(CH^- wherein m is an integer from 2 to 6; R 3 and R are each independently of the other linear or branched lower alkyl that may be substituted by Q-Qalkoxy, or aryl-lower alkyl or lower alkenyl; or R 3 and R 4 together are -(CH 2 ) z -Y r (CH 2 ) z - wherein Yj is a direct bond, -O-, -S- or -NR 1B -, and R 1B is H or lower alkyl and z is an integer from 2 to 4; and R 5 is branched Q-Qoalkylene, phenylene or phenylene substituted by from 1 to 3 methyl groups, benzylene or benzylene substituted by from 1 to 3 methyl groups, cyclohexylene or cyclohexylene substituted by from 1 to 3 methyl groups, cyclohexylene-CH 2 - or cyclo- hexylene-CH 2 - substituted by from 1 to 3 methyl groups. An especially preferred sub-group of compounds of formula I comprises those wherein R j is methyl, allyl, toluylmethyl or benzyl, R 2 is methyl, ethyl, benzyl or phenyl, or Rj and R together are pentamethylene, R 3 and R 4 are each independently of the other lower alkyl having up to 4 carbon atoms, or R 3 and R 4 together are -CH 2 CH 2 OCH 2 CH 2 -, and R 5 is branched Q-Qoalkylene, phenylene or phenylene substituted by from 1 to 3 methyl groups, benzylene or benzylene substituted by from 1 to 3 methyl groups, cyclohexylene or cyclohexylene substituted by from 1 to 3 methyl groups, cyclohexylene-CH 2 - or cyclo- hexylene-CH 2 - substituted by from 1 to 3 methyl groups. The group R 5 is especially a group in which the reactivity of a OCN group or, possibly, a NH 2 or masked NH 2 group is reduced, this being achieved essentially by steric hindrance or electronic influences at preferably one of the adjacent carbon atoms. R5 is preferably, therefore, alkylene that is branched in the α-position or especially the β-position with respect to, for example, the OCN group, or is a cyclic hydrocarbon radical that is substi¬ tuted as defined in at least one α-position. Some examples of especially preferred compounds are H 2 - p-C 6 H 4 -C(0)-C(CH 3 ) 2 -N-mθφholinyl CH 2 ) 2 -O-pC 6 H 4 -C(O)-C(CH 3 ) 2 -N-moφholinyl The compounds of formula I can be prepared in a manner known per se by reaction of dϋsocyanates with the corresponding H-acidic photoinitiators. The compounds are obtained in high yields and purity even when two H-acidic groups, for example two OH groups, of differing reactivity are present in the photoinitiator at the same time. It is especially advantageous to use diisocyanates having isocyanate groups of differing reactivity since the formation of isomers and diadducts can thereby be substantially suppressed. The differing reactivity may be brought about, for example as described hereinabove, by steric hindrance. The differing reactivity may also be achieved by masking one isocyanate group in the diisocyanate, for example as a carboxylic acid or a hydroxylamine. The invention further relates to a process for the preparation of compounds of formula (I) which comprises reacting a compound of formula II wherein X, Y, R, Rj, R , R 3 and R are as defined hereinbefore, preferably in an inert organic solvent, with a diisocyanate of formula HI or with such a diisocyanate optionally mono-masked OCN-R 5 -NCO (HI), wherein R 5 is as defined hereinbefore. Preferred examples of diisocyanates wherein the reactivity of the two isocyanato groups is distinctly different are e.g. hexane- 1,6-diisocyanate, 2,2,4-trimethylhexane-l,6-diiso- cyanate, 1 ,3-bis-(3-isocyanatopropyl)-tetramethyldisiloxane, tetramethylenediisocyanate, phenylene- 1,4-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, m- or p-xylenediisocyanate, isophoronediisocyanate, cyclohexane-l,4-diisocyanate, 1,5-naph- thylenediisocyanate, 4,4 '-diphenylmethanediisocyanate, 4,4 ' -diphenylsulfonediisocyanate or 4,4 , -dicyclohexylmethanediisocyanate. Masking agents are known from methane chemistry. They may be, for example, phenols (cresol, xylenol), lactams (e-caprolactam), oximes (acetoxi e, benzophenone oxime), H-active methylene compounds (diethyl malonate, ethyl acetoacetate), pyrazoles or benzotriazoles. Masking agents are described, for example, by Z. W. Wicks, Jr. in Pro¬ gress in Organic Coatings, 9 (1981), pages 3-28. The starting materials of the type shown in formula II are known and are described, for example, in EP-A-284561, EP-A-117 233 or EP-A-088 050. Suitable inert solvents are aprotic, preferably polar, solvents such as, for example, hydro- carbons (petroleum ether, methylcyclohexane, benzene, toluene, xylene), halogenated hydrocarbons (chloroform, methylene chloride, trichloroethane, tetrachloroethane, chloro- benzene), ethers (diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran (THF), dioxane), ketones (acetone, dibutyl ketone, methyl isobutyl ketone), carboxylic acid esters and lactones (ethyl acetate, butyrolactone, valerolactone), alkylated carboxylic acid amides (N,N-dimethylacetamide (DMA) or N,N-dimethylformamide (DMF), N-methyl-2-pyιrolidone (NMP)), nitriles (acetonitrile), sulfones and sulfoxides (dimethyl sulfoxide (DMSO), tetramethylenesulfone). Polar solvents are preferably used. The reactants are advantageously used in equimolar quantities. The reaction temperature may, for example, be from 0 to 200°C. When using catalysts, the temperatures may advan¬ tageously be in the range from -20° to 60°C and preferably in the range from -10° to 50°C. Suitable catalysts are, for example, metal salts, such as alkali metal salts, of carboxylic acids, tertiary amines, for example tri-lower alkyl amines (triethylamine, tri-n-butyl- amine), N-methylpyirolidine, N-methylmσrpholine, N,N-dimethylpiperidine, pyridine and 1,4-diaza-bicyclooctane. Tin compounds have been found to be especially effective, especially alkyltin salts of carboxylic acids, such as, for example, dibutyltin dilaurate, or, for example, tin dioctoate. If free NH groups are present in the compounds of formula I, those groups can initially be protected by suitable protecting groups during the reaction with a diisocyanate and subse¬ quently freed again by removing the protecting groups. Suitable protecting groups are known to the person skilled in the art Representative examples can be found, for example, in T.W. Greene, "Protective Groups in Organic Synthesis", Wiley Interscience, 1981. The isolation and purification of the compounds prepared are carried out in accordance with known methods, for example extraction, crystallisation, re-crystallisation or chromatographic purification methods. The compounds are obtained in high yields and purity. The yields in the case of non-optimised processes may be more than 85 % of the theoretical yields. The compounds of formula (I) are outstandingly suitable as photoinitiators for ethyleni- cally unsaturated radically polymensable compounds. In that case, the oligomers and polymers so produced carry one, two or more terminal isocyanate groups. The invention further relates to the use of a compound according to formula (I) as a photoinitiator for ethylenically unsaturated radically polymensable compounds. The compounds according to formula (I) are also outstandingly suitable for the preparation of oligomeric and polymeric photoinitiators by reaction with functional oligomers or polymers that contain active H atoms in terminal or pendant groups, for example OH or NH groups. These macromeric photoinitiators are distinguished by good tolerability and high effectiveness, the photochemical decomposition products being covalently bonded into the resulting polymers, for example as chain initiators or terminators, so that a long service life is ensured. A further advantage to be mentioned is the special structure of the photopolymers, since the polymer chains grow on the macromeric photoinitiator as terminal or pendant blocks, as a result of which additional advantageous performance properties are produced. By the choice of oligomers or polymers, therefore, it is possible to establish desired properties in the photopolymer in a controlled manner. The invention further relates to oligomers or polymers having H-active groups -OH and/or -NH- bonded to the oligomer or polymer backbone terminally (1 or 2 groups) or pendantiy (one or more groups), if desired via a bridge group, or having H-active -NH- groups bonded in the oligomer or polymer backbone, the H atoms of which H-active groups are partly or completely substituted by radicals of formula IV O -CONH— R 5 -NH-C - Y - NR 3 R 4 (IV), wherein R, Rj, R , R 3 , R 4 , R 5 , X and Y are as defined hereinbefore. The H-active groups are preferably -COOH, OH- or -NH- groups. The oligomers may have, for example, an average molecular weight of from 300 to 10000 dalton and contain preferably at least 3, more preferably from 3 to 50 and espec¬ ially from 5 to 20 structural units. As is known, the transition between oligomers and polymers is fluid and cannot be defined exactly. The polymers may contain from 50 to 10000, more preferably from 50 to 5000, structural units and may have an average molecular weight of from 10000 to 1 000000, preferably from 10000 to 5 00000. The oligomers and polymers may also comprise up to 95 mol %, preferably from 5 to 90 mol %, comonomeric structural units without H-active groups, based on the polymer. The oligomers and polymers having H-active groups may be natural or synthetic oligo¬ mers or polymers. Natural oligomers and polymers are, for example, oligo- and poly-saccharides or deriv¬ atives thereof, proteins, glycoproteins, enzymes and growth factors. Some examples are cyclodextrins, starch, hyaluronic acid, deacetylated hyaluronic acid, chitosan, trehalose, cellobiose, maltotriose, maltohexaose, chitohexaose, agarose, chitin 50, amylose, glucanes, heparin, xylan, pectin, galactan, poly-galactosamine, glycosaminoglycanes, dextran, aminated dextran, cellulose, hydroxyalkylcelluloses, carboxyalkylcelluloses, fucoidan, chondroitin sulfate, sulfated polysaccharides, mucopolysaccharides, gelatin, zein, collagen, albumin, globulin, bilirubin, ovalbumin, keratin, fibronectin and vitro- nectin, pepsin, trypsin and lysozyme. The synthetic oligomers and polymers may be substances containing the groups -COOH, -OH, -NH 2 or -NH β, wherein Rg is Cj-Qalkyl. They may be, for example, hydrolysed polymers of vinyl esters or ethers (polyvinyl alcohol); hydroxylated polydiolefins, e.g. polybutadiene, polyisoprene or polychloroprene; polyacrylic acid and polymethacrylic acid and also polyacrylates, polymethacrylates, polyacrylamides or polymethacrylamides having hydroxyalkyl or aminoalkyl radicals in the ester group or amide group; poly- siloxanes having hydroxyalkyl or aminoalkyl groups; polyethers of epoxides or glycidyl compounds and diols; polyvinylphenols or copolymers of vinylphenol and olefinic comonomers; and copolymers of at least one monomer from the group vinyl alcohol, vinylpyrrolidone, acrylic acid, methacrylic acid, or hydroxyalkyl- or aminoalkyl-contain- ing acrylates, methacrylates, or acrylamide or methacrylamide, or hydroxylated diolefins widi ethylenically unsaturated comonomers, e.g. acrylonitrile, olefins, diolefins, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene, α-methylstyrene, vinyl ethers and vinyl esters; or polyoxaalkylenes having terminal OH or aminoalkyloxy groups. Preferred oligomers and polymers are, for example, cyclodextrins having a total of from 6 to 8 glucose structural units forming a ring, or hydroxyalkyl or aminoalkyl derivatives or glucose- or maltose-substituted derivatives, of which at least one structural unit corres¬ ponds to formula (V) wherein R 7 , R 8 and R 9 are each independently of the others H, Q-Qalkyl, especially methyl, Q-Qacyl, especially acetyl, Q-Qhydroxyalkyl, especially hydroxymethyl or 2-hydroxy- eth-l-yl, C 2 -C 10 aminoalkyl and especially Q-Qaminoalkyl, for example 2-aminoeth-l-yl or 3-aminoprop-l-yl or 4-aminobut-l-yl, X is -O- or -NR 1B -, wherein, per cyclodextrin unit, a total of from 1 to 10 and preferably from 1 to 6 radicals Xj may be -NR 1B - and the remaining radicals Xj are -O-, wherein R 1B is hydrogen or lower alkyl; and at least one of the radicals R 7 , R 8 and R is a radical of formula (VI) O O R, - R 10 — CONH R 5 - NH- C - Y - X ^- C - C NR 3 R 4 (VI) wherein R, R , R 2 , R 3 , 4 , R 5 , X and Y are as defined hereinbefore, and R O is a direct bond, -(Q-Qalkylene-0)- or -(Q-C 0 alkylene-NH)-, wherein the hetero atom is linked to the carbonyl in formula (VI). In a preferred embodiment, from at least half the glucose units to all 6 to 8 of the glucose units contain at least one radical of formula (VI). Also preferred is an embodiment in which only one glucose unit carries a radical of formula (VI). For R, R , R 2 , R 3 , R 4 , R 5 , X and Y the preferred definitions given above apply. RJO is preferably a direct bond, -CH 2 -O-, -CH 2 CH 2 -O-, -CH 2 CH 2 -NH- or -CH 2 CH 2 CH 2 -NH-. Other preferred oligomers and polymers are, for example, oligo- and poly-siloxanes having OH or NH 2 groups in alkyl, alkoxyalkyl or aminoalkyl terminal groups or side- chains, the H atoms of which are substituted by a photoinitiator according to die invention. They may be random or block oligomers or random or block polymers. More preferred are those oligomers and polymers which comprise a) from 5 to 100 mol % structural units of formula (VII) 13 and b) from 95 to 0 mol % structural units of formula (VIII) based on the oligomer or polymer, wherein RJJ is Q-Qalkyl, lower alkenyl, cyano-lower alkyl or aryl each unsubstituted or partly or completely substituted by F, and is preferably methyl, ethyl, vinyl, allyl, cyanopropyl or trifluoromethyl, Rj 2 is Q-Qalkylene, preferably 1,3-propylene, -(CH 2 ) z -(0-CH 2 -CHCH 3 -) z -, -(CH z -(0-CH 2 -CΗό z - or -(CH 2 ) z -NH-(CH 2 ) z -NH-, preferably -(CH 2 ) 3 -(0-CH 2 -CHCH 3 -) 2 - or -(CH 2 ) 3 -NH-(CH 2 ) 2 -NH-, wherein z is independently of the other an integer from 2 to 4, R 1 has the same definitions as Rj j or is -R 1 -Xj-H or -R 12 -Xj-R 15 -H, R j 3 is a radical of formula (IX) O R, ■ CONH — Rg- NH-C - Y - X - C - NR 3 R 4 (TX), R 9 R wherein R, Rj, R 2 , R 3 , R 4 , R 5 , X and Y are as defined hereinbefore, and Rj 5 is a direct bond or a group -C(0)-(CHOH) r -CH 2 -O- wherein r is 0 or an integer from 1 to 4. For R, R J , R 2 , R 3 , R 4 , R 5 , X and Y the preferred definitions given above apply. X is preferably -NH-. Preferred oligomeric and polymeric siloxanes are also those of formula (X) wherein R JJ is Q-Qalkyl, vinyl, allyl or phenyl each unsubstituted or partly or completely substi¬ tuted by F, and is preferably methyl, R 12 is Q-Qalkylene, preferably 1,3-propylene, R 14 has the same definitions as RJJ or is -R 1 -X j -H or -R 12 -X J -RJ 5 -H, s is an integer from 1 to 1000 and preferably from 1 to 100, and R 13 is a radical of the above formula (DC) wherein R, Rj, R 2 , R 3 , R 4 , R 5 , X and Y are as defined hereinbefore, and R j5 is a direct bond or a group -C(0)-(CHOH) r -CH 2 -O- wherein r is 0 or an integer from 1 to 4. For R, Rj, R 2 , R 3 , R 4 , R 5 , X and Y the preferred definitions given above apply. Xj is preferably -NH-. Other preferred oligomers and polymers are those based on oligovinyl and polyvinyl alcohol in which the H atoms in the OH groups are partly or completely substituted by a radical of formula (VI). They may be homopolymers with -CH 2 CH(OH)- structural units or copolymers with other monovalent or bivalent structural units of olefins. More preferred are those oligomers and polymers which comprise a) from 5 to 100 mol % structural units of formula (XI) and b) from 95 to 0 mol % structural units of formula (XII) wherein R 16 is a radical of die above formula (VI) wherein R, R , R 2 , R 3 , R^ R 5 , X and Y are as defined hereinbefore and R 10 is a direct bond, -(Q-Qalkylene-O)- or -(C 2 -Q 0 - alkylene-NH)-; R 17 is H, Cι-C 6 alkyl, -COOR 20 or -COO Θ , Rj 8 is H, F, Cl, CN or Q-Qalkyl, and R 19 is H, OH, RJO-H, F, Cl, CN, R 20 -O-, Q-Q 2 alkyl, -COO θ , -COOR 20 , -OCO-R 20 , methylphenyl or phenyl, wherein R 20 is Q-Qgalkyl, Q-Qcycloalkyl, (Q-Q 2 alkyl)- C 5 -Qcycloalkyl, phenyl, (Cj-Cj 2 alkyl)phenyl, benzyl or (Cj-Cj 2 alkyl)benzyl. Rj 7 is preferably H. When R 17 is alkyl, it is preferably methyl or ediyl. When R 17 is -COOR- 20 , R* 2 o is preferably Cj-C 12 alkyl, especially Q-Qalkyl. When R 18 is alkyl, it is preferably Q-Qalkyl, e.g. methyl, ethyl, n-propyl or n-butyl. R 18 is preferably H, Cl or Q-Qalkyl. When Rj is the group R 2 o-0-, R^ is preferably Cj-C 12 alkyl, especially Cj-C 6 alkyl. When R 19 is alkyl, it preferably contains from 1 to 6, especially from 1 to 4, carbon atoms. When R 9 is the group -COOR- 20 , R- 20 is preferably C 1 -C 12 alkyl, especially Q-Qalkyl, or cyclo- pentyl or cyclohexyl. When R 1 is the group -OCO-R 20 , R 2 o is preferably Q-Q 2 alkyl, especially C j -C 6 alkyl, or phenyl or benzyl. In a preferred embodiment, R 17 is H, R 18 is H, F, Cl, methyl or ethyl, and R 19 is H, OH, F, Cl, CN, Q-Qalkyl, Q-Qalkoxy, Q-Qhydroxyalkoxy, -COO-Q -Qalkyl, -OOC-C j -C 6 alkyl or phenyl. Especially preferred are those oligomers and polymers wherein R 17 is H, R 18 is H or methyl, and R J9 is H, OH, CN, methyl, OCH 3 , 0(CH 2 ) t OH or -COOCH 3 , and t is an integer from 2 to 6. Another preferred group of oligomers and polymers comprises partially or completely hydroxyalkylated oligo- or poly-acrylates or -methacrylates, or -acrylamides or -meth- acrylamides, in which the primary hydroxy group or amino group, respectively, is substi¬ tuted by a radical of the above formula (DC). They may comprise, for example, from 5 to 100 mol % structural units of formula (XIII) and from 95 to 0 mol % structural units of formula (XTV) wherein R 1 is H or methyl, X and X 3 are each independendy of the other -O- or -NH-, R %2 , is -(CH 2 ) C - and c is an integer from 2 to 12, preferably from 2 to 6, R- 23 is a radical of formula (DC), R 7 and R 18 are as defined hereinbefore, and R 24 has the same definitions as Rj 9 or is -C(0)X R 22 X 3 H. For R^, R 17 , R 18 and R 19 the preferred definitions mentioned hereinbefore apply. For X and X 3 die preferred definitions mentioned hereinbefore apply. Other preferred oligomers and polymers are tfiose consisting of polyalkylene oxides in which the H atoms of the terminal OH or -NH 2 groups are partly or completely substituted by radicals of formula (IX). They may, for example, be those of formula (XV) having identical or different structural repeating units -[CH CH(R 26 )-O]- R-25 [(CH 2 CH-0-) u ] v — R 27 -X 4 -R 28 (XV), R 26 wherein R- 25 is the group R^-X^ or is the v-valent radical of an alcohol or polyol having from 1 to 20 carbon atoms, R- 26 is H, Q-C 8 alkyl, preferably Q-Qalkyl and especially methyl, R 27 together with X is a direct bond or R 27 is Q-Qalkylene, preferably Q-Qalkylene and especially 1,3-propylene, X 4 is -O- or -NH-, R^ is a radical of formula (DC), u is independendy of die other a numerical value from 3 to 10000, preferably from 5 to 5000, especially from 5 to 1000 and more especially from 5 to 100, and v is an integer from 1 to 6, preferably from 1 to 4. R- 25 may be a mono- to tetra-valent radical of an alcohol or polyol. When R 25 is the radical of an alcohol, R-y is preferably linear or branched Q-Qo-alkyl or -alkenyl, Q-Q- and especially Q-Q-cycloalkyl, -CH 2 -(Q-Qcycloalkyl), C 6 -C 10 aryl and especially phenyl and naphthyl, Q-Qgaralkyl and especially benzyl and l-phenyledι-2-yl. The cyclic or aromatic radicals may be substituted by Q-Q 8 alkyl or Q-Q 8 alkoxy. When R- 25 is the radical of a diol, R- 25 is preferably branched and especially linear Q-Qo¬ alkylene or alkenylene and more preferably C 3 -Q 2 alkylene, Q-Q- and especially Q-Q- cycloalkylene, -CH 2 -(Q-Qcycloalkyl)-, -CH 2 -(C 5 -C 6 cycloalkyl)-CH 2 -, C 7 -Q 6 aralkylene and especially benzylene, -C_H 2 -(Q-QoaryI)-CH 2 - and especially xylylene. The cyclic or aromatic radicals may be substituted by Q-Q 2 alkyl or Q-Q 2 alkoxy. When R 25 is a trivalent radical, it is derived from aliphatic or aromatic triols. R- 25 is prefer¬ ably a trivalent aliphatic radical having from 3 to 12 carbon atoms that is derived espec¬ ially from triols having preferably primary hydroxy groups. Most preferably, R 25 is -CH 2 (CH-)CH 2 -, HC(CH 2 -) 3 or CH 3 C(CH 2 -) 3 . When R^ is a tetravalent radical, it is derived preferably from aliphatic tetrols. R- 25 is in that case preferably C(CH 2 -) 4 . Preferably, R- 25 is a radical derived from Jeffamins (Texaco), a Pluriol, a Poloxamer (BASF) or poly(tetramethylene oxide). For R 28 die preferred definitions mentioned hereinbefore apply. Especially prefeired are homo-oligomers and homo-polymers and block oligomers and block polymers each having structural units of the formula -[CH 2 CH 2 -O]- or -[CH 2 CH(CH 3 )-O]-. Also suitable are fluorinated polyethers corresponding to formula (XVI) R 25 — [(CF 2 CF-O-) J v — R 27 -X 4 -R 28 (XVI), Rd wherein R 27 , R 28 , X 4 , u and v are as defined hereinbefore, R- 25 is as defined hereinbefore or is the monovalent radical of a partly fluorinated or per-fluorinated alcohol having from 1 to 20, preferably from 1 to 12 and especially from 1 to 6 carbon atoms, or the bivalent radical of a partly fluorinated or per-fluorinated diol having from 2 to 6, preferably from 2 to 4 and especially 2 or 3 carbon atoms, and R < ι is F or perfluoroalkyl having from 1 to 12, preferably from 1 to 6 and especially from 1 to 4 carbon atoms. R d is especially -CF 3 . Other suitable oligomers and polymers are, for example, polyamines, for example poly- vinylamine, or polyethyleneiimnes, in which the H atoms of the NH groups are substituted by a radical of formula (VI), including the preferences already mentioned. Also suitable is poly-€-lysine. The oligomers and polymers according to die invention can be prepared simply and in a manner known per se by reaction of a compound of formula (I) with HO- or NH-funct- ional oligomers and polymers. The photoinitiators of formula (I) according to die invention can also be used for the preparation of polymerisable photoinitiators having ethylenically unsaturated groups by reacting a compound of formula (I) with OH- or NH-functional ethylenically unsaturated compounds. That reaction is known to one skilled in the art and will not be described in more detail. OH- and NH-functional ediylenically unsaturated compounds are, for example, (hydroxyalkyl)- or (aminoalkyl)-acrylic or -methacrylic acid esters or amides. The invention further relates to compounds of formula (XVII) (XVII), wherein X, Y, R, Rj, R 2 , R 3 , R and R 5 have die definitions given hereinbefore, including the preferred definitions, and R- 29 is a vinylic, radically polymerisable hydrocarbon having from 2 to 12 carbon atoms or is a radical of formula (XVDI) wherein R 30 is H or methyl, R 31 is branched or, preferably, linear Q-Q 2 alkylene, lower alkylenearylene or arylene- lower alkylene, or, when w = 0, R 31 may be a bond, w is zero or 1 and X 5 and X 6 are each independendy of the otiier -O- or -NH-. R 31 is preferably Q-Qalkylene, for example ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene and 1,6-hexylene. When R 29 is a vinylic, radically polymerisable hydrocarbon, it is, for example, alkenyl, vinylphenyl or vinylbenzyl as a radically polymerisable group having preferably from 2 to 12 carbon atoms. Examples of alkenyl are vinyl, allyl, l-propen-2-yl, l-buten-2- or -3- or -4-yl, 2-buten-3-yl, and die isomers of pentenyl, hexenyl, octenyl, decenyl, undecenyl and dodecenyl. R 29 contains preferably from 2 to 12, especially from 2 to 8, carbon atoms. In a preferred definition, widiin the scope of this invention R 29 is alkenyl having from 2 to 4 carbon atoms. Some examples are: The compounds of formula (I) or (XVII) are outstandingly suitable as initiators for radiation-induced polymerisation of ethylenically unsaturated compounds. In the process, compounds according to formula (XVII) are incorporated into the polymers in their entirety or as fragments either via die unsaturated group and/or via the radicals formed. The oligomers and polymers according to the invention are also eminendy suitable as initiators, it being possible to form graft polymers or also, depending upon die content of initiator groups in the macroinitiator, inter-penetrating and unconnected or only partially inter-connected polymer networks. The invention further relates to dimeric photoinitiators of formula (XDC) O R C - C - NR 3 R 4 (XDC), wherein E 2 is -Xι-(CH 2 ) m -Xj- and each Xj independendy of the other is -O- or -NH- and m is an integer from 2 to 6, q is zero or 1, R 32 is a radical of formula (XX) wherein X, Y, R, Rj, R , R 3 , R t and R 5 have die definitions given hereinbefore, including the preferred definitions. In a preferred embodiment, Xj is eidier only -O- or only -NH-. In a highly preferred embodiment, Xj is -O- and D j is -NHCO-, the carbonyl group of Dj being linked to E 2 . In a more highly preferred embodiment, X is -O-, q is zero and Dj is -NHCO-, the carbonyl group of D j being linked to E^ The invention further relates to trimeric photoinitiators of formula (XXI) {R 33 -E 3 -} 3 -T (XXI), wherein R 33 is a compound of formula (XXII) -f Dg- Rg-J-NK NR 3 R 4 (XXII), wherein X, Y, R, Rj, R 2 , R 3 , RJ and R 5 have the definitions given hereinbefore, including die preferred definitions, q is independendy of the otiier zero or 1, D 2 is -NHCO-, -CONH- or -NHCONH-, E 3 is lower alkylene and T is a trivalent organic or inorganic radical. In a preferred embodiment, E 3 is hexamethylene, each q is zero and T is a trivalent organic radical and, more preferably, is cyanuric acid less its 3 acidic hydrogen atoms. Within the scope of die present invention, hereinbefore and hereinafter and unless stated odierwise, arylene is preferably phenylene or napthylene each unsubstituted or substituted by lower alkyl or lower alkoxy, especially 1,3-phenylene, 1,4-phenylene or methyl- 1,4- phenylene, or 1,5-naphthylene or 1,8-naphthylene. Within die scope of die present invention, aryl has up to 24, and preferably up to 18, carbon atoms and is a carbocyclic aromatic compound that is unsubstituted or substituted by lower alkyl or lower alkoxy. Examples are phenyl, toluyl, xylyl, methoxyphenyl, tert- butoxyphenyl, naphthyl or phenanthryl. Within the scope of this invention, unless defined odierwise die term "lower" used in connection widi radicals and compounds denotes especially radicals or compounds having up to 8 carbon atoms, preferably up to 6 carbon atoms. Lower alkyl has especially up to 8 carbon atoms, preferably up to 6 carbon atoms, and is, for example, methyl, etiiyl, propyl, butyl, teit-butyl, pentyl, hexyl or iso-hexyl. Lower alkenyl is linear or branched alkenyl having from 2 to 8 carbon atoms, preferably from 2 to 6 carbon atoms and especially from 2 to 4 carbon atoms. Examples of alkenyl are vinyl, allyl, l-propen-2-yl, l-buten-2- or -3- or -4-yl, 2-buten-3-yl, and the isomers of pentenyl, hexenyl or octenyl. Unless defined odierwise, alkylene has up to 10 carbon atoms and may be straight-chain or branched. Suitable examples include decylene, octylene, hexylene, pentylene, butylene, propylene, ethylene, methylene, 2-propylene, 2-butylene or 3-pentylene. Alkylene is preferably lower alkylene. Lower alkylene is alkylene having up to 8, and especially up to 6, carbon atoms. An especially preferred definition of lower alkylene is methylene or ethylene. The arylene unit of alkylenearylene or arylenealkylene is preferably phenylene that is unsubstituted or substituted by lower alkyl or lower alkoxy; the alkylene unit thereof is preferably lower alkylene, such as methylene or ethylene, especially methylene. Prefer¬ ably, such radicals are therefore phenylenemethylene or methylenephenylene. Lower alkoxy has especially up to 8 carbon atoms, preferably up to 6 carbon atoms, and is, for example, methoxy, ethoxy, propoxy, butoxy, tert-butoxy or hexyloxy. Within the scope of the present invention, aryl-lower alkyl has up to 30, preferably up to 24, and especially up to 18, carbon atoms and is lower alkyl substituted by aryl. Examples of aryl-lower alkyl are benzyl, xylylmethyl, toluylethyl, phenylbutyl, tert-butoxyphenyl- methyl, naphthylpropyl, methoxyphenylmethyl or phenylhexyl. The invention further relates to a radiation-sensitive composition comprising a) at least one ethylenically unsaturated photo-polymerisable or photo-crosslinkable compound (hereinafter referred to as radiation-sensitive organic material) and b) an effective initiator quantity of at least one compound of formula (I), (XVII), (XIX) or (XXI) or of an oligomer or polymer having structural units of formula (TV). The compounds of component b) may be present in an amount of from 0.001 to 70 % by weight, especially from 0.001 to 50 % by weight, more especially from 0.01 to 40 % by weight and most especially from 0.01 to 20 % by weight, based on component a). The amount is mainly governed by die photoactive groups bonded in the initiator, die fewer that are present, the greater is the chosen amount to be added. Ed ylenically unsaturated photo-crosslinkable compounds and therewith also photo- structurisable materials are known. Such materials have been described, for example, by G. E. Green et al. in J. Macromol. Sci.; Revs. Macromol. and Chem., C21(2), 187-273 (1981 to 1982) and by G.A. Delzenne in Adv. Photochem., 11, pp. 1-103 (1979). The radiation-sensitive organic material is preferably a monomeric, oligomeric or polymeric substance having photo-polymerisable ethylenically unsaturated groups, espec¬ ially a non-volatile or not readily volatised substance of that kind. Photo-polymerisable compounds are, for example, acrylic and especially mediacrylic acid esters of alcohols and polyols, or acrylic and especially methacrylic acid amides of amines and polyamines, for example Q-Q 8 alkanols, ethylene glycol, propanediol, butanediol, hexanediol, di(hydroxymethyl)cyclohexane, polyoxyalkylenediols, for example di-, tri- or tetra-ethylene glycol, di- or tri-l,2-propylene glycol, trimethylol-mediane, -ethane or -propane and pentaery thritol, C j -Cjgalkylamines, ethylenediamine, diediylenetriamine and triethylenetetramine, which can be used alone, in mixtures or in admixture widi binders. Also suitable are mono-, oligo- and poly-siloxanes having acrylic and especially meth¬ acrylic acid ester radicals that are bonded to pendant or terminal hydroxy(Q-Q 2 alkyl) or amino(Q-C 2 alkyl) groups, for example l-trimethylsilyl-3-methacroyloxypropane, l-pentame yldisUoxanyl-3-memacτyloxyprop_me and 3-[tris(t-_imethylsiloxy)silyl]-propyl mediacrylate. Also suitable are perfluoroalkyl acrylates and methacrylates. The photo-polymerisable compounds may comprise otiier additives customary for processing or application, and, in addition, other conventional photoinitiators or photo- sensitizers. The photo-polymerisation is carried out under die effect of radiation in die absence or presence of a solvent, preferably UV radiation, it being possible to use known radiation sources, for example mercury vapour lamps. If solvents are used, they are preferably inert solvents already mentioned by way of example above. A compound according to formula (I) can also be bonded to surfaces of inorganic or organic materials (hereinafter referred to as substrates) that contain H-active -COOH, HO-, HS- or -NH- groups. Suitable mediods for this are known, for example immersion, spraying, brushing, knife-coating, pouring, rolling and especially spin-coating or vacuum vapour deposition mediods. A compound according to formula (I) is firmly anchored to die surface by reaction with die isocyanate group. This reaction may be carried out, for example, at elevated temperatures, for example from 0° to 100°C and preferably at RT. After the reaction, excess compounds can be removed, for example, with solvents. There can tiien be applied to the modified surfaces photo-polymerisable compounds which are subsequendy polymerised under die effect of radiation and firmly bound to the substrate by graft polymerisation by way of the photoinitiators. In the process, a tentacle-like or brush-like polymer structure is formed on die surface of the substrate, which is capable of substantially preventing the undesirable formation of irreversible deposits of, for example, proteins, lipids or salts in the biological medium (membrane fouling, lime deposits). Suitable substrates are, for example, types of glass, silicate minerals (silica gels), metal oxides and, especially, natural or synthetic plastics which are known in great number. Some examples of plastics are polyaddition and polycondensation plastics (polyurethanes, epoxy resins, polyethers, polyesters, polyamides, polyimides); vinyl polymers (poly¬ acrylates, polymethacrylates, polystyrene, polyethylene and its halogenated derivatives, polyvinyl alcohol (PVA), polyhydroxyethyl methacrylate, polyvinyl acetate and poly- acrylonitrile); elastomers such as silicones, polybutadiene or polyisoprene, or polybutadiene cross-linked with a polysiloxane, optionally upon which a vinylic monomer is graft-polymerised; unmodified or modified bio-polymers (collagen, cellulose, chitosan and previously mentioned bio-polymers). When substrates contain too few or no functional groups, it is possible to modify die surface of the substrates by methods known per se, for example plasma methods or oxidation or hydrolysis methods, and generate functional groups such as -OH, -NH 2 or -CO 2 H. The invention further relates to a material consisting of (a) an inorganic or preferably organic substrate to which (b) there is bonded as photoinitiator at least one compound of formula (I), which is firmly bound to the substrate by way of O atoms, S atoms, HN-Cj-Qalkyl groups or NH groups, on the one hand, and by die isocyanate group of the photoinitiators, on the other hand, and, optionally, (c) a thin layer of a polymer on die photoinitiator layer, which polymer can be obtained by applying a thin layer of photo- polymerisable ethylenically unsaturated substances to the substrate surface provided widi photoinitiator radicals and polymerisation of die layer of ethylenically unsaturated substances by irradiation, preferably with UV radiation. The said material is preferably a biomedical material and, especially, an ophdialmic moulded article consisting of a transparent organic base material, for example a contact lens or an intraocular lens, especially a contact lens. The layer thickness of the ethylenically unsaturated substances depends mainly upon die desired properties. It may be from 0.001 μm to 1000 μm, preferably from 0.01 μm to 500 μm, more preferably from 0.1 to 100 μm, especially from 0.5 to 50 μm and most especially from 1 to 20 μm. For the production of contact lenses specifically, a layer thick¬ ness of from 0.01 to 50 μm, preferably from 0.05 to 20 μm and especially from 0.1 to 5 μm is desirable. The layers can be produced by the coating mediods mentioned herein¬ before. The ethylenically unsaturated substances may be the compounds mentioned hereinbefore as photo-polymerisable compounds. Other suitable ethylenically unsaturated compounds are non-volatile substituted polyolefins, especially acrylic acid or methacrylic acid and tiieir esters and amides, for example acrylic and methacrylic acid Q-Q 2 alkyl esters or oligooxaalkylene esters or Q-Q 2 hydroxyalkyl esters or amides (2,3-dihydroxypropyl methacrylate, N,N-dimethylacrylamide, acrylamide, N,N-diethylaminoethyl methacrylate, oligoethylene oxide acrylates and methacrylates, 2-hydroxyethylmethacrylic acid esters, methyl methacrylate (MMA), polyethylene glycol 1000 diat has been derivatised widi from 1 to 2 molar equivalents of methacrylic acid (PEG(IOOO)MA), and N-vinylpyrroli- done. The invention further relates to a process for modifying surfaces of inorganic or organic substrates tiiat contain H-active HO-, HS-, HN-Q-Qalkyl groups or -NH 2 - groups, comprising the steps of a) applying to the substrate a thin layer of a photoinitiator of at least one compound of formula (I), where appropriate together with a catalyst, for example dibutyltin dilaurate, b) where appropriate heating the coated material and washing off the excess photoinitiator, c) applying a thin layer of a photo-polymerisable ethylenically unsaturated substance to die substrate surface provided widi said photoinitiator, and d) irradiating the layer containing the ethylenically unsaturated substance preferably with UV radiation. Any non-covalendy bonded polymers that may be formed can be removed after the poly¬ merisation, for example by treatment with suitable solvents. By die process according to the invention the surfaces can be modified in many ways and given particular properties for different uses. Depending upon the ethylenically unsatu¬ rated substances chosen it is possible to improve in a controlled manner, for example, mechanical properties, for example surface hardness, scratch-resistance, wettability, abrasion resistance, writability, colorability, adhesive strength of coatings and of coverings of various metal, ceramic or polymer materials, sliding properties, stability of liquid films, resistance to undesirable deposits and colonisation by microorganisms, and physical properties such as, for example, coefficient of friction, permeability to gases, liquids and dissolved inorganic or organic substances of low to high molecular weight, and transparency, an especially strong adhesion of die polymer layers being a special advantage. The photoinitiators according to the invention and substrates modified by die photo- initiators are distinguished by a high chemical and photochemical reactivity. They may be used to form photoreactive materials that may be employed as coating materials, photo- structurisable materials, for composite materials and, especially, as materials for biomedical applications, for example contact lenses and surgical materials. The materials are especially suitable for the production of hydrophilic and biocompatible surfaces on contact lenses by graft polymerisation widi die formation of a tentacle structure (brush structure) that is especially beneficial in terms of required properties. Of particular importance are the high wettability and die maintenance of a stable film of moisture on the surface, for example a lachrymal fluid film on the surface of a contact lens. Also of great importance is the improvement of the behaviour in biological systems, for example an improved biocompatibility, protection against bio-erosion, prevention of plaque formation and of bio-fouling, and no blood clotting or toxic or allergic reactions. The modified materials according to the invention are especially suitable for the produc¬ tion of contact lenses. With regard to contact lenses, the following improvements in properties are especially important: high wettability (small contact angle), high tear strength, good lubricating effect, high abrasion resistance, no or only negligible enzymatic degradation, no deposition of components from the lachrymal fluid (proteins, lipids, salts, cell degradation products), no affinity for cosmetics, volatile chemicals, such as solvents, dirt and dust, no attachment or nesting-in of microorganisms, and sliding properties for movement of die lens on die eye. The materials modified in accordance widi die invention are also suitable for the produc¬ tion of artificial blood vessels and odier biomedical materials for prostheses, for surgery and for diagnostics, it being especially advantageous tiiat endothelial cells can grow over these materials. The invention further relates to a contact lens comprising (a) a transparent organic base material having functional groups, especially hydroxy, mercapto, amino, alkylamino or carboxy groups, and (b) a thin layer on the surface, consisting of constituents that are preferably derived from (bl) at least one photoinitiator of formula (I) and (b2) a graft polymer formed by photo-copolymerisation of an olefin. The invention further relates to a contact lens comprising (a) a transparent organic base material having functional groups, especially hydroxy, mercapto, amino, alkylamino or carboxy groups, and (b) a tiiin layer on the surface, consisting of constituents that are preferably derived from at least one photoinitiator of formula (I) which is bonded to a functional group of die base material via an isocyanate group. Suitable base materials (a) are, for example, unmodified or modified natural polymers, for example collagen, chitosan, hyaluronic acid and cellulose esters, such as cellulose acetate or cellulose butyrate. Suitable base materials are, for example, unmodified or modified syndietic polymers, for example polyvinyl alcohol, polyhydroxyetiiyl methacrylate, poly- glyceryl methacrylate, and copolymers based on those polymers. Also suitable are natural and syndietic polymers, for example polymers having silicone, perfluoroalkyl and or alkyl acrylate structural units, in which functional groups are generated on the surface by suitable methods, for example plasma treatment, etching or oxidation. Suitable olefins of the above-mentioned graft polymer (b2) are, for example, acrylamide, N,N-dimethylacrylamide, methacrylamide, hydroxyetiiyl methacrylate, glyceryl meth¬ acrylate, oligoethylene oxide mono- and bis-acrylates, ethylene glycol dimethacrylate, methylene bisacrylamide, vinylcaprolactam, acrylic acid, methacrylic acid, fumaric acid monovinyl ester, vinyl trifluoroacetate and vinylene carbonate, it being possible for reactive esters to be subsequently hydrolysed if required. In certain cases, it may be advantageous to use mixtures of two or more photoinitiators according to the invention. Mixtures with known photoinitiators can, of course, also be used, for example mixtures with benzophenone, acetophenone derivatives, bezoin ethers or benzil ketals. To accelerate the photo-polymerisation amines may be added, e.g. triethanolamine, N-methyl-diethanolamine, p-dimethylaminobenzoic acid ethyl ester or Michler's ketone. The action of die amines can be intensified by die addition of aromatic ketones of the benzophenone type. The photo-polymerisation can also be accelerated by the addition of photo- sensitizers, which shift or broaden die spectral sensitivity. These are especially aromatic carbonyl compounds, for example derivatives of benzophenone, thioxanthone, anthraquinone and 3-acylcoumarin, and 3-(aroylmethylene)-dιiazolines. The effectiveness of the photoinitiators according to die invention can be increased by die addition of titanocene derivatives having fluoro-organic radicals, as are described in EP-A-122,223 and EP-A-186,626, for example in an amount of from 1 to 20 %. Examples of such titanocenes are bis(methylcyclopentadienyl)-bis(2,3,6-trifluorophenyl)-titanium, bis(cyclopentadienyl)-bis(4-dibutylamino-2,3,5,6-tetrafluorophenyl)-titanium, bis(methyl- cyclopentadienyl)-2-(trifluoromethyl)phenyl-titanium isocyanate, bis(cyclopentadienyl)- 2-(trifluoromethyl)phenyl-titanium trifluoroacetate or bis(methylcyclopentadienyl)-bis- (4-decyloxy-2,3,5,6-tetrafluorophenyl)-titanium. Liquid α-aminoketones are especially suitable for these mixtures. In addition to die photoinitiator, the photo-polymerisable mixtures may contain various additives. Examples of die latter are thermal inhibitors, which are intended to prevent premature polymerisation, such as, for example, hydroquinone or sterically hindered phenols. In order to increase the dark storage stability, it is possible to use, for example, copper compounds, phosphorus compounds, quaternary ammonium compounds or hydroxylamine derivatives. For the purpose of excluding atmospheric oxygen during die polymerisation paraffin or similar waxy substances may be added which migrate to the surface when polymerisation commences. As light-protecting agents it is possible to add, in small quantities, UV absorbers, for example those of die benzotriazole, benzophenone or oxalanilide type. Better still is the addition of light-protecting agents that do not absorb UV light, such as, for example, sterically hindered amines (HALS). The photoinitiators according to the invention can be used for various other purposes. Their use in unpigmented, pigmented or coloured systems is also of importance, such as, for example, for printing inks, for photographic reproduction processes, image recording processes and for the manufacture of relief moulds. Anodier important field of application comprises coating compositions, which may be pigmented or unpigmented. The mixtures are especially useful in white paints, by which TiO 2 -pigmented coating compositions are understood. Other fields of application are radiation-curing of photoresists, the photo-crosslinking of silver-free films and die production of printing plates. Anodier use is for outdoor paints the surface of which subsequendy cures in daylight. The photoinitiators are advantageously used for the applications mentioned in amounts of from 0.1 to 20 % by weight, preferably approximately from 0.5 to 5 % by weight, based on the photo-polymerisable composition. The polymerisation is carried out in accordance widi die known methods of photo- polymerisation by irradiation widi light high in short-wave radiation. Suitable light sources are, for example, mercury medium-pressure, high-pressure and low-pressure radiators, super-actinic fluorescent tubes, metal halide lamps or lasers, the emission maxima of which lie in the range from 250 to 450 nm. In the case of a combination with photo-sensitizers or ferrocene derivatives, it is also possible to use longer-wavelengtii light or laser beams up to 600 nm. According to die invention, die compounds of formula I, XVΕ, XDC or XXI or oligomers or polymers having structural units of formula IV can be used as photoinitiators for the photo-polymerisation of ethylenically unsaturated compounds and mixtures that comprise such compounds. The unsaturated compounds may contain one or more olefinic double bonds. They may be of low molecular weight (monomeric) or of higher molecular weight (oligomeric). Examples of monomers having one double bond are alkyl or hydroxyalkyl acrylates or methacylates, for example methyl, ediyl, butyl, 2-etiιylhexyl or 2-hydroxy- ethyl acrylate, isobornyl acrylate, methyl or ethyl methacrylate. Other examples of tiiese are acrylonitrile, acrylamide, methacrylamide, N-substituted (medι)acrylamides, vinyl esters, such as vinyl acetate, vinyl ethers, such as isobutyl vinyl ether, styrene, alkyl- and halo-styrcnes, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride. Examples of monomers having more than one double bond are ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexametiiylene glycol diacrylate or bisphenol-A diacrylate, 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylol- propane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinyl- benzene, divinyl succinate, diallyl phdialate, triallyl phosphate, triallyl isocyanurate or tris(2-acryloyloxyethyl) isocyanurate. Examples of higher-molecular-weight (oligomeric) poly-unsaturated compounds are acryl- ated epoxy resins, acr lated polyethers, acrylated polyurethanes or acrylated polyesters. Other examples of unsaturated oligomers are unsaturated polyester resins, which are usually prepared from maleic acid, phthalic acid and one or more diols and have molecular weights of approximately from 500 to 3000. Such unsaturated oligomers can also be called pre-polymers. Often used are two-component mixtures of a pre-polymer with a poly-unsaturated monomer or three-component mixtures that contain, in addition, a mono-unsaturated monomer. The pre-polymer is in this case primarily responsible for the properties of die coating film. By varying it, the person skilled in the art can influence the properties of die cured film. The poly-unsaturated monomer acts as a crosslinker which makes the coating film insoluble. The mono-unsaturated monomer acts as a reactive diluent by means of which the viscosity is reduced widiout the necessity to use a solvent. Such two-component and three-component systems based on a pre-polymer are used botii for printing inks and for surface coatings, photoresists or other photo-curable composi¬ tions. One-component systems based on photo-curable pre-polymers are also widely used as binders for printing inks. Unsaturated polyester resins are mostiy used in two-component systems together widi a mono-unsaturated monomer, preferably with styrene. For photoresists, specific one-component systems are often used, for example polymaleimides, polychalkones or polyimides as described in DE-OS 2 308 830. The unsaturated compounds can also be used in admixture widi non-photo-polymerisable film-forming components. These may be, for example, physically drying polymers or solutions thereof in organic solvents, such as, for example, nitrocellulose or cellulose acetobutyrate. They may also, however, be chemically or thermally curable resins, such as, for example, polyisocyanates, polyepoxides or melamine resins. The concomitant use of thermally curable resins is important for the use in so-called hybrid systems which are photo-polymerised in a first step and crosslinked by thermal after-treatment in a second step. The Examples given below serve to illustrate the present invention in more detail; they are not, however, intended to limit die scope thereof in any way. Unless stated otherwise, temperatures are given in degrees Celsius. Example A 1 2-Dimethylamino-2-benzyl-l-(4-(2-hydroxyethoxy)phenyl)-butan-l-one. The tide compound is prepared in accordance widi the synthesis described in EP-A- 284561. Example A2 2-Ethyl-2-dimediylamino-l-(4-(2-hydroxyedioxy)phenyl)-pent-4-en-l-one. The tide compound is prepared in quantitative yield analogously to Example Al. Yellow¬ ish crystals of m.p. 80 - 82°C remain. Example A3 2-Emyl-2-dimethylamino-l-(4-(2-hydroxyedιoxy)phenyl)-pentan-l-one. 32.6 g (0.11 mol) of 2-ethyl-2-dimethylamino-l-(4-(2-hydroxyedιoxy)phenyl)-pent-4- en-l-one according to Example A2 are dissolved in 220 ml of ethyl acetate, 1.6 g of palladium-on-carbon (5 %) are added thereto and die mixture is tiien hydrogenated at 30°C under normal pressure. After approximately 3 hours die absorption of hydrogen ceases (2.58 litres, 103 % of the theoretical amount). The catalyst is removed by filtration and die solvent is distilled off using a rotary evaporator (RE). The oily residue is purified by flash-chromatography (petroleum edier/ediyl acetate 2:1). 27.4 g (84 %) of a slightly yellowish oil remain. Example A4 1 -(4-(2-Hydroxyedιyldιio)phenyl)-2-methyl-2-moιpholino-propan- 1 -one. HO The preparation of the tide compound is described in EP-A-088 050. Example A5 l-(4-(2-Hydroxyethoxy)phenyl)-2-methyl-2-morpholino-propan-l-one. The tide compound is prepared analogously to Example A4. Example A6 Preparation of a dimeric photoinitiator: In a 250 ml flask equipped widi reflux condenser, thermometer, stirrer and nitrogen inlet pipe, 5.8 g (20 mmol) of 2-ethyl-2-dimethylamino-l-(4-(2-hydroxyetiιoxy)phenyl)-pent- 4-en-l-one (from Example A2) and 2.2 g (10 mmol) of isophorone diisocyanate (IPDI) are dissolved in 100 ml of dry methylene chloride. 0.6 g (1 mmol) of die catalyst dibutyltin dilaurate (DBTDL) is added tiiereto and die batch is stirred at room temperature (RT) for 26 hours. The course of the reaction is monitored by thin-layer chromatography (TLC) (silica gel TLC plates, eluant petroleum ether / ethyl acetate 1:2). The reaction solution is then stirred into water, and die organic phase is separated off and washed twice more with water. The organic phase is dried over MgS0 and concentrated using a RE. The residue which remains is purified by flash-chromatography (petroleum ether / ethyl acetate 1:1). 6.3 g (78 %) of a viscous yellow oil remain. Combustion analysis yields the following values: Q^O^ (805.07) calc. C 68.63 H 8.51 N 6.96 found C 68.31 H 8.64 N 6.98 Examples A7. A8. A9 and A 10 Analogously to Example A6, the following dimeric photoinitiators are each prepared by reaction of 2 equivalents of a photoinitiator from Examples Al, A3, A4 and A5 and 1 equivalent of IPDI. All the structures are verified by proton NMR. Example R softening range Example All Preparation of: In a 250 ml flask equipped widi reflux condenser, thermometer, stirrer and nitrogen inlet pipe, 8.8 g (30 mmol) of 2-ethyl-2-dimethylamino-l-(4-(2-hydroxyedιoxy)phenyl)- pentan-1-one (from Example A3) and 3.15 g (15 mmol) of 2,2,4-trimethylhexametiιylene diisocyanate (2,2,4-TMDI) are dissolved in 100 ml of dry methylene chloride. 0.95 g (1.5 mmol) of die catalyst DBTDL is added diereto and die batch is stirred under reflux for 14 hours. The course of the reaction is monitored by IR spectroscopy (IR band of die isocyanate group disappears at 2250 cm' 1 ). The reaction solution is then cooled to RT and stirred into water. The organic phase is separated off and washed twice more with water. The organic phase is dried over MgSO 4 and concentrated using a RE. The residue which remains is purified by flash-chromatography (petroleum ether / ethyl acetate 2:1).7.3 g (61 %) of a viscous oil remain. The structure is verified by proton NMR. Example A 12 Analogously to Example Al 1, by reaction of 2 equivalents of the photoinitiator from Example A5 with 1 equivalent of diphenylmethane 4,4 '-diisocyanate in methylene chloride and with the addition of 0.1 equivalent of DBTDL, the following compound is prepared: A beige powder having a softening range of 70 - 82°C is obtained. Example A 13 Analogously to Example Al 1, by reaction of 2 equivalents of die photoinitiator from Example A4 with 1 equivalent of hexamethylene diisocyanate in methylene chloride and widi the addition of 0.1 equivalent of DBTDL, the following compound is prepared: A yellowish resin is obtained in 98 % yield. Example A 14 Analogously to Example Al 1, by reaction of 2 equivalents of the photoinitiator from Example A5 with 1 equivalent of toluene 2,4-diisocyanate (TDI) in methylene chloride and widi die addition of 0.1 equivalent of DBTDL, the following compound is prepared: A beige powder having a softening range of 83 - 90°C is obtained. Example A15 Analogously to Example Al 1, by reaction of 3 equivalents of die photoinitiator from Example A5 with 1 equivalent of Desmodur®3390 in methylene chloride and widi the addition of 0.1 equivalent of DBTDL, the following compound is prepared: A beige powder having a softening range of 60 - 67°C is obtained. Example A 16 Analogously to Example Al 1, by reaction of 3 equivalents of the photoinitiator from Example Al with 1 equivalent of Desmodur® 3390 in methylene chloride and widi die addition of 0.1 equivalent of DBTDL, the following compound is prepared: A yellowish resin is obtained. Example A 17 Preparation of the following compound: In a 100 ml flask equipped widi reflux condenser, thermometer, stirrer and nitrogen inlet pipe, 2.92 g (10 mmol) of 2-ethyl-2-dimethylamino-l-(4-(2-hydroxyethoxy)phenyl)-pent- 4-en-l-one (from Example A2) are dissolved in 30 ml of dry methylene chloride, and die solution is mixed widi 2.22 g (10 mmol) of IPDI dissolved in 30 ml of dry methylene chloride. 2.0 mg of the catalyst DBTDL arc added thereto and stirring is carried out at RT for 72 hours. The course of the reaction is monitored by TLC (eluant is toluene / acetone 6: 1). The reaction solution is then stirred into water. The organic phase is separated off and washed twice more with water. The organic phase is dried over MgSO 4 and concen¬ trated using a RE. The residue which remains is purified by column chromatography (toluene / acetone 6:1). 3.4 g (66 %) of a yellow oil remain. The structure is verified by proton NMR, IR and elemental analysis. Example Al 8 Analogously to Example A 17, die following isocyanate is prepared from 1.17 g (4 mmol) of l-(4-(2-hydroxyedioxy)phenyl)-2-mediyl-2-morpholino-propan-l-one (from Exam¬ ple A5) and 0.7 g (4 mmol) of 2,4-TDI using DBTDL as catalyst in methylene chloride. After die addition of 50 ml of etiier and 200 ml of petroleum ether to die RM, the target compound precipitates in crystalline form. It is filtered off, washed widi petroleum ether and dien dried in vacuo to yield die compound below of m.p. 97 - 102°C. Examples A19. A20 and A21 Analogously to Example A17, the following compounds are prepared: wherein R is one of the following radicals: O Example No. A19 .. . -o- JL N Example No. A20 Example No. A21 Example A22 Analogously to Example A17, the following compound is prepared: Example A23: Analogously to Example A 17, the following isocyanate is prepared from 5.1 g (29.3 mmol) of 2,4-toluene diisocyanate (TDI) and 10 g (29.3 mmol) of 2-dimethyl- amino-2-benzyl-l-(4-(2-hydroxyedιoxy)phenyl)-butan-l-one (from Example Al) using DBTDL as catalyst in methylene chloride. The RM is diluted widi 500 ml of diethyl ether and 2 litres of petroleum ether, whereupon die product precipitates. It is filtered off, washed widi diediyl etiier / petroleum ether and dried in vacuo. A beige powder having a softening range of 99 - 103°C is obtained. Example B 1 Preparation of an oligomeric photoinitiator whereiinn R= and x:y is approximately 27:1, and n is 5. 0.7 g (1.3 mmol) of die isocyanate from Example A 17, 20 ml of dry methylene chloride and 2.55 g (0.51 mVal NH 2 / g) of aminoalkylpolysiloxane KF 8003 (Shin Etsu, Japan) are placed in an apparatus according to Example A 17. The reaction mixture is stirred at RT for 2 hours and at 40°C for 20 minutes. The solvent is tiien removed using a RE. The residue is freed of solvent residues under a high vacuum (40°C, 0.001 mbar (0.1 Pa)). The tide compound is obtained in quantitative yield. In the IR spectrum, there is no OCN band. Example B2 Analogously to Example Bl, an oligomeric photoinitiator having the structure according to Example Bl is prepared from 0.76 g (1.3 mmol) of isocyanate from Example A21 and 2.55 g (0.51 mVal NH 2 / g) of aminoalkylpolysiloxane KF 8003 (Shin Etsu, Japan), wherein R has the following definition: Exa ple B3 Analogously to Example Bl, an oligomeric photoinitiator having the following structure is prepared from 0.55 g (0.97 mmol) of isocyanate from Example A20 and 1.47 g (0.7 mVal NH 2 / g) of aminoalkylpolysiloxane X-22-161B (Shin Etsu, Japan): wherein x is approximately 38, and R corresponds to die radical of the tide compound of Example A20 less die isocyanate. Example B4 Analogously to Example Bl, a solution of 1.0 g (1.95 mmol) of die isocyanate from Example A 17 in 20 ml of dry acetonitrile is mixed with 2.24 g (0.84 mVal NH 2 / g) of Jeffamin ED 2001 (Texaco, USA) in 30 ml of dry acetonitrile and die mixture is stirred at RT for 24 hours. After working-up, 3.2 g (99 %) of the following photoinitiator are obtained: R-NHCONH-CHCΗ 3 CH 2 -(C<_HCH 3 CH 2 ) a -(OCH 2 CH 2 ) b -(OCHCH 3 CH 2 ) c -NHCONH-R wherein a + c = 2.5 and b ■ = 40.5, and R corresponds to the radical of the title compound of Example A17 less the isocyanate. Example B5 In an apparatus according to Example A17, 1.65 g of polyvinyl alcohol (PVA) (Serva® 03/20, molecular weight approximately 13 000) are dissolved at 80°C under nitrogen in dry NMP. The solution is tiien cooled to RT and a solution of 1.0 g (1.88 mmol) of the isocyanate from Example A 19 in 10 ml of dry NMP, and 5 mg of DBTDL as catalyst are added diereto. This mixture is then heated at 40°C for 48 hours. After that time, no OCN is detectable by IR at 2250 cm 1 . The RM is cooled to RT and 700 ml of diethyl ether are added diereto, the product precipitating. After filtration, washing with diethyl edier and dien drying under a high vacuum, 1.9 g of a white product remain which, according to elemental analysis, comprises 2.20 % S. Proton NMR is consistent with the following structure: -[(CH 2 -CΑOH) Λ -(CΑ 2 -CΑO(X>NHR) h ] n - wherein n is approximately 10 and a:b = 20:1; and R corresponds to die radical of die tide compound of Example A 19 less the isocyanate. Examples B6. B7 and B8 Analogously to Example B5, two hydroxyalkyl-substituted polydimethylsiloxanes (KF-6002 / KF-6001) and one dextran are reacted widi the isocyanate from Example A19. The following parameters describe tiiose compounds. The yields are approximately 90 % in all cases. The sulfur content of those compounds is determined by combustion analysis (last column of die Table). solvent S-content (%) calc. / found THF 1.50/ 1.38 2.22/ 2.08 DMSO 1.08 /0.99 Analogously to Example B5, 3.23 g of collagen (Serva 17440, MW ~ 80000) are dissolved in DMSO over the course of 12 hours and then 1.0 g (1.9 mmol) of isocyanate from Example A20 in 10 ml of DMSO is added. After stirring die reaction mixture at RT for 72 hours, it is diluted widi 500 ml of methanol, whereupon die product precipitates. The product is filtered off and washed repeatedly widi dry THF. It is then dried under a high vacuum (0.1 Pa, RT, 72 hours). 2.8 g of a yellow-white product remain, die IR spectrum and proton NMR of which are consistent with die expected structure. The Production of Polymer Films and Contact Lenses Example Cl 5 g of poly(l,2-syndiotactic)-butadiene (PB) from Poly sciences Inc. (Catalogue No. 16317, MW * 10000) are dissolved at 40°C in 100 ml of THF. The solution is then cooled to RT and poured onto a Folanorm sheet (Folex®, Zurich, Switzerland) to produce a film of a PB solution of approximately 0.5 mm thickness. The THF is slowly evaporated at RT under nitrogen. The polybutadiene film which remains is tiien extracted widi etiianol and dried until its weight is constant Example C2 2.2 g of PB arc dissolved in 50 ml of methylcyclohexane at 40°C under nitrogen. A solution of 2 g of H-siloxane (Experimental Product K-3272, Goldschmidt, Germany) in 5 ml of mediylcyclohexane is added thereto and stirring is carried out for 5 minutes. This solution is then gassed widi nitrogen for 30 minutes. There are then added to tiiis solution 3 drops of the catalyst platinum divinyltetramethyldisiloxane (ABCR, PC 072) dissolved in 1 ml of methylcyclohexane and die mixture is then heated at 50°C, with stirring, for 3 minutes. This mixture is en placed between two glass plates to produce a liquid film of approximately 1.5 mm thickness. This sandwich system is then heated at 60°C under nitrogen for 16 hours. It is then cooled to RT, die glass plates are removed and die cross- linked polybutadiene film is extracted widi THF. After extraction, the crosslinked poly¬ butadiene film is dried until its weight is constant. Example C3 5.35 g (1 mmol) of vinyl-containing polysiloxane (Silopren U Additiv V 200, Bayer Leverkusen, Germany) are mixed widi 1.13 g (2 mmol) of H-siloxane (Experimental Product 1085, Goldschmidt, Germany) and die mixture is stirred at RT under reduced pressure (200 mbar (20kPa)) for one hour. Nitrogen is then bubbled through the mixture for 30 minutes, 2 drops of the catalyst platinum divinyltetramethyldisiloxane (ABCR, PC 072) are added and the mixture is stirred for 5 minutes. Polypropylene (PP) moulds (Ciba Vision Adanta, for moulded articles of 0.5 mm diickness) are then filled widi tiiis mixture, closed and heated in an oven at 60°C under nitrogen for 16 hours. The moulds are allowed to cool to RT and are opened, and die disks so produced, which contain cross¬ linked polyvinylsiloxane, are extracted widi ethanol and subsequendy dried until their weight is constant Example C4 Contact lenses consisting of crosslinked polyvinylsiloxane are produced analogously to Example C3, using polypropylene moulds suitable for the production of soft contact lenses having a thickness of 100 μm, a diameter of 1.4 cm and a base curve of 8.4 mm. Example C5 2.63 g (0.5 mmol) of vinyl-containing polysiloxane (Silopren U Additiv V 200) and 3.0 g of H-siloxane (Experimental Product K 3272, Goldschmidt, Germany) are mixed and stirred at RT under reduced pressure (200 mbar (20kPa)) for one hour. Nitrogen is then bubbled through the mixture for 30 minutes, 2 drops of die catalyst platinum divinyltetra¬ methyldisiloxane (ABCR, PC 072) are added and die mixture is stirred for 10 minutes. Polypropylene contact lens moulds (Ciba Vision Adanta, USA) are then filled widi tiiis mixture, closed and heated in an oven at 60°C under nitrogen for 16 hours. The moulds are allowed to cool to RT and are opened, and die contact lenses so produced, which contain crosslinked polyvinylsiloxane, are extracted with edianol and subsequendy dried until tiieir weight is constant Example DI 4 g of photoinitiator from Example A17 are dissolved under nitrogen in 10 ml of acetone. A portion of this solution is sprayed onto a polybutadiene film according to Example Cl, so that, after die acetone has been evaporated while flushing with nitrogen, an even photo¬ initiator film is produced on die polybutadiene film. The coated polybutadiene film is then irradiated widi UV light (12 mW/cm 2 ) for 10 minutes. The film is subsequendy washed three times with acetone in order to remove non-bonded photoinitiator. The film is then dried under reduced pressure (0.001 bar (0.1 Pa)) until its weight is constant The Fourier- transform IR spectrum (FT-IR) of the film exhibits an OCN band at 2250 cm' 1 . Finally, die film is immersed for 2 hours in a 5 % Jeffamin M 2070 solution in acetone and is tiien thoroughly washed twice with acetone and three times widi deionised water. The poly¬ butadiene film so coated is analysed in FT-IR and tiien the contact angles are determined (K 12, Kriiss GmbH, Hamburg, Germany). polybutadiene film Cl contact angle in [°] advancing receding uncoated 102 78 coated 66 47 Example D2 Analogously to Example DI, a crosslinked polybutadiene film from Example C2 is coated. polybutadiene film C2 contact angle in [°] advancing receding uncoated 111 71 coated 96 59 Example D3 Analogously to Example DI, a polybutadiene film from Example Cl is coated widi die photoinitiator from Example A 19. polybutadiene film Cl contact angle in [°] advancing receding uncoated 102 78 coated 62 46 Example D4 Analogously to Example DI, contact lenses from Example C4 are coated widi die photo¬ initiator from Example A 19. polyvinylsiloxane C4 contact angle in [°] advancing receding uncoated 111 78 coated 98 34 Example D5 Analogously to Example DI, a crosslinked polyvinylsiloxane disk from Example C3 is coated widi die photoinitiator from Example A 17. disk from C3 uncoated coated Example D6 Analogously to Example DI, a polybutadiene film according to Example Cl is coated with the photoinitiator from Example A17. In contrast to Example DI, however, this film is then immersed in a DMSO solution comprising 1 % Dextran 8 (Serva) and approxi¬ mately 1 mg of DBTDL as catalyst. polybutadiene film Cl contact angle in [°] advancing receding uncoated 102 78 coated 98 51 Example D7 Analogously to Example DI, a polybutadiene film according to Example Cl is coated with die photoinitiator from Example A17. In contrast to Example DI, however, this film is then immersed in an aqueous solution comprising 5 % polyethyleneimine (Fluka). polybutadiene film Cl contact angle in [°] advancing receding uncoated 102 78 coated 66 18 Example D8 Analogously to Example DI, contact lenses according to Example C5 are coated widi die photoinitiator from Example A17. In constrast to Example DI, however, these lenses are then immersed in an aqueous solution comprising 5 % polyethyleneimine (Fluka). contact lenses from C5 contact angle in [°] advancing receding uncoated 115 80 coated 99 56 Example El 2 g of the macrophotoinitiator according to Example B5 are dissolved in 50 ml of dry DMSO. Nitrogen is bubbled through this solution for 30 minutes. A polybutadiene film from Example Cl (2 x 2 cm) is then immersed in this solution for 10 minutes, then removed and irradiated widi UV light (12 mW/cm 2 ) for 10 minutes. The film so coated is washed once widi DMSO, twice with isopropanol, once with 50 % aqueous isopropanol and once widi water. The film is men dried and analysed (layer diickness of the hydro- philic film is approximately 6 μm, determined by means of optical microscopy and RuO 4 contrasting. polybutadiene from Cl contact angle in [°] advancing receding uncoated 102 78 coated 48 37 Example E2 Analogously to Example El, a crosslinked polybutadiene film from Example C2 is treated widi the macrophotoinitiator from Example B5. polybutadiene from C2 contact angle in [°] advancing receding uncoated 111 71 coated 97 38 Example E3 Analogously to Example El, siloxane disks from Example C3 are treated with the macro¬ photoinitiator from Example B8. siloxane disks from C3 contact angle in [°] advancing receding uncoated 112 72 coated 94 36 Example E4 Analogously to Example El, contact lenses from Example C4 are treated with the macro¬ photoinitiator from Example B5. contact lenses from C4 contact angle in [°] advancing receding uncoated 111 78 coated 88 37 Example E5 Analogously to Example El, contact lenses from Example C5 are treated widi die macro¬ photoinitiator from Example B8. contact lenses from C5 contact angle in [°] advancing receding uncoated 115 70 coated 76 41 Example Fl Polyvinylsiloxane contact lenses according to Example C3 are placed in a plasma reactor. The reactor chamber is then charged widi argon for 1 minute under glow discharge condi¬ tions and then with 1,2-diaminocyclohexane under die following conditions: radio frequency of 27.12 MHz, 30 Watt output, 0.3 mbar (30 Pa) pressure, flow rate of operating gas 3.65 cm 3 / min (STP), residence time of die lenses in die reactor is 5 minutes. The reactor is then flushed widi nitrogen and die lenses are removed. Example F2 The contact lenses treated according to Example Fl are immersed for 30 minutes at room temperature (RT) and under nitrogen in an acetonitrile solution comprising 1 % by weight of the photoinitiator from Example A 17. The reactive photoinitiator is thereby bonded to the amino groups generated on die surface of the lenses by the plasma treatment. The contact lenses are subsequendy washed with acetonitrile for 12 hours and tiien dried in vacuo for 3 hours. Example F3 1.5 g (20 mmol) of acrylamide are dissolved in 10 ml of distilled water in a round- bottomed flask with stirring at RT and gassing with nitrogen. This solution is then de-gassed under reduced pressure and tiien gassed widi nitrogen again for 30 minutes. The solution is then filtered (pore size 0.45 μm) and a sufficient quantity is poured into a petri dish for contact lenses from Example F2, placed in that solution, to be covered by about 1 mm of die solution. Irradiation (12 mW/cm 2 ) is then carried out from both sides for 3 minutes using a mercury high-pressure lamp (2000 Watt). The lenses are then removed from the bath and washed repeatedly widi water. Extraction is then carried out for a further 24 hours with HPLC-water. The lenses are dried in vacuo and tiien analysed by FT-IR, AFM and contact angle measurement. Examples F4, F5, F6 and F7 Contact lenses from Example F2 comprising a covalently bonded photoinitiator are modi¬ fied analogously to Example F3 using, in place of acrylamide (AA), aqueous solutions of other monomers. The contact angles of those contact lenses before and after such a coating are reproduced in die following Table. contact angle in [°] untreated treated advancing receding advancing receding AA = acrylamide, NVP = N-vinyl-2-pyrrolidone, HEMA = hydroxyediyl mediacrylate, PEG(1000)MA = methacrylic acid tiiat has been derivatised once or twice with poly¬ ethylene glycol 1000, DMA = N,N-dimethylacrylamide. Example Gl 0.3 g of macrophotoinitiator from Example Bl is dissolved under nitrogen in 0.4 g of dry THF. To the solution are added 0.2 g of freshly distilled NVP and 0.1 g of ethylene glycol dimethacrylate (EGDMA) and stirring is carried out for 15 minutes. Gassing with nitrogen is then carried out for 30 minutes. The solution is then filtered (pore size 0.45 μm) into a bottle. Under nitrogen, clean PP moulds are filled widi tiiis solution (180 to 200 μl per mould), and the moulds are closed and irradiated widi UV light (12 mW/cm 2 ) for 15 minutes. The moulds are opened and die mould halves, containing the lenses, are placed in an ethanol bath, whereupon the lenses separate from the mould halves. The lenses are then extracted in ethanol for a further 24 hours and are subsequendy dried in vacuo. Example G2 Analogously to Example Gl, lenses are produced from 40 g of macrophotoinitiator from Example B 1, 15 g of DMA, 5 g of EGDMA and 40 g of THF. Example G3 Analogously to Example Gl, lenses are produced from 34.5 g of macrophotoinitiator from Example Bl, 59.5 g of 3-[tris(trimethylsiloxy)silyl]-propyl methacrylate (TRIS) and 6 g of NVP, the TRIS and NVP acting as solvents for the photoinitiator. The radiation time for this mixture is 20 minutes. Example G4 Analogously to Example G3, lenses are produced from 57 g of macrophotoinitiator from Example Bl, 37 g of 3- [tris(trimethylsiloxy)silyl] -propyl methacrylate (TRIS) and 3 g of NVP and 3 g of EGDMA. The following Table gives information on the properties of the contact lenses so produced. Example G5 0.16 g of macrophotoinitiator from Example B5 are dissolved under nitrogen in 0.82 g of a solution of N-methylpyrrolidone (NMP) in DMSO (70:12). 20 μg of the crosslinker EGDMA are added and gassing widi nitrogen is carried out for 20 minutes. The solution is then filtered (Teflon filter of pore size 0.45 μm) into a botde. Under nitrogen, clean PP moulds are filled widi tiiis solution (180 to 200 μl per mould), and die moulds are closed and irradiated widi UV light (12 mW/cm 2 ) for 30 minutes. The moulds are opened and die mould halves, containing the lenses, are placed in an edianol bath, whereupon the trans¬ parent, slightly yellow lenses separate from the mould halves. The lenses are then extrac¬ ted in ethanol for a further 24 hours and are subsequendy dried in vacuo. Example G6 Analogously to Example G5, contact lenses are produced from 0.1 g of macrophoto¬ initiator from Example B5, 0.5 g of DMSO, 0.4 g of NVP and 20 μg of EGDMA. Example G7 0.25 g of macrophotoinitiator from Example B8 are dissolved under nitrogen in 0.5 g of dry DMSO. 0.25 g of HEMA and 20 μg of die crosslinker EGDMA are added and gassing with nitrogen is subsequently carried out for 30 minutes. The solution is then filtered (pore size 0.45 μm) and introduced under nitrogen into clean PP moulds. Irradiation and working-up are carried out as described in Example G5. 2.0 g of macroinitiator from Example B3 arc dissolved under nitrogen in 3 g of dry THF. 2 g of this solution are mixed widi 0.9 g of freshly distilled NVP and gassing with nitrogen is carried out for 30 minutes. Under nitrogen, clean PP moulds are then filled with this solution (approximately 200 μl of solution per mould), closed and irradiated widi UV light (12 mW/cm 2 ) for 10 minutes. The moulds containing the highly viscous polymer solution are then freed of THF in a drying cupboard at 40°C. Clear, slighdy yellow disks diat are soluble in ethanol remain. Example G9 Analogously to Example G8, transparent, slightly opaque disks are produced from a mixture of 2.0 g of macroinitiator from Example B3 and 0.9 g of DMA. Example Hl In a sulfonating flask, 0.31 g (1.88 mmol) of 2-aminoethyl methacrylate hydrochloride are introduced into 10 ml of dry acetonitrile with stirring. There are then added drop wise under nitrogen, simultaneously but from different dropping funnels, 1.0 g (1.88 mmol) of reactive photoinitiator from Example A 19 dissolved in 10 ml of dry acetonitrile and 190 mg (1.88 mmol) of triethylamine dissolved in 5 ml of dry acetonitrile. Stirring is carried out at RT for a further 72 hours. The course of die reaction is monitored during that time widi TLC. The reaction mixture is then poured onto 100 ml of water, the mixture is stirred and tiien extraction is carried out 3 times widi toluene. The organic phase is separated off, dried and concentrated using a RE. The residue is purified by chroma¬ tography on silica gel (toluene / acetone 8:2). The IR spectrum, the proton NMR and elemental analysis are consistent with the structure. In an apparatus analogous to Example HI, 0.46 g (3.5 mmol) of HEMA are introduced into 10 ml of acetone and there are then added at RT under nitrogen, with stirring, 1.97 g (3.5 mmol) of photoinitiator from Example A20 dissolved in 10 ml of acetone. To this are added 10 μg of dibutyl-p-cresol as inhibitor and 10 μg of DBTDL as catalyst The reaction mixture is then stirred at 40°C under nitrogen for 24 hours. During that time, the isocyanate group disappears from the IR spectrum. The RM is concentrated using a RE and die residue is purified by chromatography on silica gel. Example H3 In an apparatus analogous to Example HI, 0.5 g (0.97 mmol) of photoinitiator from Example A23 are introduced into 5 ml of methylene chloride. There are then added at RT under nitrogen, with stirring, 0.13 g (0.97 mmol) of HEMA dissolved in 3 ml of methylene chloride. After the addition of 10 μg of dibutyl-p-cresol as inhibitor and 10 μg of DBTDL as catalyst, the solution is stirred at RT for a further 48 hours. The isocyanate group disappears during that time (IR monitoring). The RM is concentrated using a RE and the residue is purified by chromatography on silica gel (toluene / acetone 8:2). Example H4 In a brown round-bottomed flask equipped with reflux condenser, tiiermometer, stirrer and argon inlet pipe, 2.0 g (3.0 mmol) of the compound from Example HI are dissolved in 12 ml of toluene and tiien mixed with 6 g (60 mmol) of MMA. 0.2 g of the initiator azoisobutyronitrile (AIBN) is added thereto. This solution is heated at 60°C for 20 hours. It is then cooled to RT, diluted with 20 ml of toluene, and 2000 ml of diethyl ether are added thereto, whereupon a solid precipitates. The solid is filtered off, washed witii a small amount of diediyl ether and dried in vacuo. A white powder remains, the proton NMR of which is consistent with the following structure, the ratio of a:b being 1:20. Example H5 Analogously to Example H4, a copolymer is prepared from 0.65 g (1 mmol) of die polymerisable photoinitiator from Example H3, 1 g (10 mmol) of MMA and 1.0 g of TRIS. Example H6 320 mg of macroinitiator from Example H4 are dissolved under nitrogen in 1.4 ml of dry THF. To the solution there are added 85 mg of freshly distilled NVP and 30 mg of EGDMA and stirring is carried out for 15 minutes. Gassing with nitrogen is then carried out for 30 minutes. This solution is filtered (filter of 0.45 μm pore size). Clean PP moulds are filled under nitrogen widi the filtered solution (approximately 200 μl of solution per mould). The moulds are closed and irradiated widi UV light (12 mW/cm 2 ) for 10 minutes. The moulds are opened, and die mould halves, containing the lenses, are placed in a THF bath, whereupon die lenses separate from the mould halves. After extraction with THF, the clear, transparent lenses are dried and analysed The water absorption is 8.1 %. Example II The photo-curing of a blue printing ink will be described. First, a blue printing ink is prepared according to the following recipe: 62.5 parts Setalin®AP 565 (urethane acrylic resin from Synthese, Holland), 15 parts 4,4'-di(β-acryloyloxyethoxy)diphenylpropane-2,2 (Ebecryl®150, UCB, Belgium) 22.5 parts Irgalithblau®GLSM (CIBA-GEIGY AG, Basle). The mixture is homogenised and milled to a particle size of < 5 μm in a three-roll mill. 5 g portions of this printing ink are each homogeneously mixed widi die desired amount of photoinitiator on a disk rubbing machine under a pressure of 180 kg/m 2 with water cooling. Samples comprising 3 % photoinitiator (based on the printing ink) are prepared. Offset prints of those printing inks are made widi a sample printing machine (from Prufbau, FRG) on 4 x 20 cm strips of art paper. The printing conditions are: printing ink coverage: 1.5 g/cm 2 pressing pressure (linear pressure): 25 kp/cm printing speed: 1 m/sec A print roller having a metal surface (aluminium) is used for this. The printed samples are cured in a UV irradiation device produced by PPG, using a lamp and an energy of 80 W/cm. The irradiation time is varied by varying the transport speed of die sample. Surface drying of die printing ink is tested immediately after irradiation by the so-called transfer test. In tiiat test, a white paper is pressed against the printed sample under a linear pressure of 25 kp/cm. If the paper remains ink-free, the test has been passed. If visible amounts of ink are transferred to die test strip, this is an indication tiiat the surface of the sample has not yet cured sufficiendy. The following Table gives the maximum transport speed at which die transfer test was still passed. To test die full curing of the printing ink, offset prints are also made as described above, except that print rollers having a rubber surface are used and die metal side of aluminium-coated paper strips is printed. The irradi¬ ation is carried out as described above. Immediately after the irradiation, the full curing is tested in a REL full cure testing device. In tiiat test, an aluminium cylinder covered with cloth is placed on die printed sample and rotated once about its own axis within 10 seconds under a pressure of 1220 g cm 2 . If visible damage occurs on the sample, the printing ink has not full-cured sufficiendy. The following Table gives the maximum trans¬ port speed at which die REL test is still passed. Example 12 Reactivity of a resist formulation. A photo-curable formulation is prepared by mixing die following components: 10 g dipentaerythritol monohydroxypentaacrylate (SR 399, Sartomer Co., Berkshire GB) 15 g tripropylene glycol diacrylate (Sartomer Co., Berkshire GB) 15 g N-vinylpyrrolidone, Fluka 10 g trismethylpropane triacrylate, Degussa 50 g urcthane acrylate Actylan AJ 20, Sociέtέ National des Poudres et Explosifs 0.3 g levelling auxiliary Byk 300, Byk-Mallinckrodt. Portions of tiiis composition are mixed widi 2 % (based on the solids content) of a photo¬ initiator (according to die following Table). These samples are applied to a 300 μm thick aluminium foil. The thickness of the dry layer is 60 μm. To that film there is applied a 76 μm thick polyester film onto which is laid a standardised test negative having 21 steps of differing optical density (Stouffer step wedge). The sample is covered with a second UV-transparent sheet and pressed by vacuum onto a metal plate. Exposure is carried out for 20 seconds at a distance of 30 cm by means of a 5 kW MO 61 metal halide lamp. After the exposure, the sheet and mask are removed and the exposed layer is developed in ethanol for 10 seconds at 23°C in an ultrasound bath. Drying is carried out at 40°C for 5 minutes in a circulating air oven. The sensitivity of the initiator system used is characterised by giving the last wedge step imaged without stickiness. The higher is the step number, the more sensitive is the tested system. In a second test series, the procedure described above is followed, except that, in addition to die 2 % of a photoinitiator (according to die Example mentioned), 0.2 % of isopropyl- thioxanthone (Quantacure ITX, International Bio-Synthetics) is added as sensitizer to the photo-curable mixture. The results of the two test series are summarised in die following Table. It will be seen that the reactivity of the photoinitiators can be increased by the addition of a small amount of the Quantacurc ITX sensitizer.

Claims: What is claimed is: 1. A compound of formula (I) O O R, II D — R δ — NH-C - Y- X —— ^j --cC - C NR 3 R 4 (I) wherein X is bivalent -0-, -NH-, -S-, lower alkylene or N Y is a direct bond or -0-(CΑ^) n - wherein n is an integer from 1 to 6 and die terminal CH 2 group of which is linked to the adjacent X in formula (I); R is H, Q-Q 2 alkyl, Q-Q 2 alkoxy, Q-Q 2 alkylNH- or -NR 1A R 1B wherein R 1A is lower alkyl and R 1B is H or lower alkyl; Rj is linear or branched lower alkyl, lower alkenyl or aryl-lower alkyl; R 2 independendy of Rj has die same definitions as Rj or is aryl, or R and R 2 togedier are -(CH 2 ) m - wherein m is an integer from 2 to 6; R 3 and R are each independendy of die other linear or branched lower alkyl that may be substituted by Q-Qalkoxy, or aryl-lower alkyl or lower alkenyl; or R 3 and R 4 togedier are -(CH 2 ) Z -Yj-(CH 2 ) Z - wherein Yj is a direct bond, -O-, -S- or -NR 1B -, and R 1B is H or lower alkyl and z is independendy of die otiier an integer from 2 to 4; R5 is linear or branched Q-Qgalkylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy- substituted Q-Qoarylene, or unsubstituted or Q-Qalkyl- or Q-Qϊdkoxy-substituted Q-Qgaralkylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted Q- J -Q 4 - arylenealkylenearylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted Q-Q- cycloalkylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted Q-Qcycloalkyl- ene-C y H 2y - or unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted -C y H 2y -(Q-Cg- cycloalkylene)-C y H 2y -, wherein y is an integer from 1 to 6; and D is an isocyanato group. 2. A compound according to claim 1, wherein X is -O-, -NH-, -S- or lower alkylene, preferably -O- or -S- and especially -0-. 3. A compound according to claim 1, wherein, in the context of die definition of Y, the index n is 1 to 5, preferably 2 to 4 and more preferably 2 or 3. 4. A compound according to claim 1, wherein Y is a direct bond. 5. A compound according to claim 1, wherein the group R as alkyl, alkoxy, alkylNH- or -NR 1A Rj B contains from 1 to 6 and preferably from 1 to 4 carbon atoms. 6. A compound according to claim 1, wherein the group R is H. 7. A compound according to claim 1, wherein R is allyl, benzyl or linear Q-Qalkyl. 8. A compound according to claim 1, wherein R 2 has the same definitions as R j . 9. A compound according to claim 1, wherein R 2 is linear lower alkyl having from 1 to 4 carbon atoms. 10. A compound according to claim 1, wherein R 2 is aryl. 11. A compound according to claim 1, wherein R and R 2 togedier are -(CH^,-,-, and m is die integer 4 or 5 and preferably 5. 12. A compound according to claim 1, wherein R 3 is linear lower alkyl having from 1 to 4 carbon atoms, benzyl or allyl. 13. A compound according to claim 1, wherein R 4 is linear lower alkyl having from 1 to 4 carbon atoms. 14. A compound according to claim 1, wherein R 3 and R 4 together are -(CH 2 ) Z -Yj-(CH 2 ) Z - wherein Yj is a direct bond, -O- or -N(CH 3 )- and z is the integer 2 or 3. 15. A compound according to claim 1, wherein R 3 and R 4 together are -(CH 2 ) Z -Y j -(CH 2 ) Z - wherein Y j is a direct bond or -O- and z is 2. 16. A compound according to claim 1, wherein R 5 is linear or branched Q-Q 8 alkylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted C 6 -C 10 arylene, unsubstituted or C j -C alkyl- or Q-Qalkoxy-substituted Cj 3 -C 24 arylenealkylenearylene or unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted Q-Qcycloalkylene, and preferably linear or branched Q-Q alkylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted Q-Qoarylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted Q 3 -Q 4 arylene- alkylenearylene or unsubstituted or Q-Qalkyl- or Cj-Qalkoxy-substituted Q-Qcyclo- alkylene. 17. A compound according to claim 1, wherein Rj is linear lower alkyl, lower alkenyl or aryl-lower alkyl; R 2 independendy of R j has die same definitions as Rj or is aryl, R 3 and R 4 are each independendy of die otiier linear or branched lower alkyl that may be substituted by Q-Qalkoxy, or aryl-lower alkyl or lower alkenyl; or R 3 and R_χ together are -((_Η 2 ) Z -Y 1 -(CH 2 ) Z - wherein Yj is a direct bond, -O-, -S- or -NR 1B -, and R 1B is H or lower alkyl and z is an integer from 2 to 4; and R 5 is linear or branched Q-Qgalkylene, unsubstimted or Q-Qalkyl- or Q-Qalkoxy- substituted Q-Qoarylene, or unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted Q-Qgaralkylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted Q 3 -Q 4 - arylenealkyleneaiylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted Q-Qcycloalkylene, unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted Q-Qcyclo- alkylene-C y H 2y - or unsubstituted or Q-Qalkyl- or Q-Qalkoxy-substituted -C y H - - cycloalkylene^C y H -, wherein y is an integer from 1 to 6. 18. A compound according to claim 1, wherein X is bivalent -O-, -NH-, -S- or -(CH^-; Y is a direct bond or -0-(CR^) n - wherein n is an integer from 1 to 6 and die terminal CH 2 group of which is linked to the adjacent X in formula (I); R is H, Q-Q 2 alkyl or Q-Q 2 alkoxy; Rj is linear lower alkyl, lower alkenyl or aryl-lower alkyl; R 2 independendy of Rj has die same definitions as Rj or is aryl, or Rj and R 2 togedier are -(CH^- wherein m is an integer from 2 to 6; R 3 and R are each independendy of die other linear or branched lower alkyl that may be substituted by Q-Qalkoxy, or aryl-lower alkyl or lower alkenyl; or R 3 and ^ together are -(CH- 2 ) Z -Y j -(CH 2 ) Z - wherein Yj is a direct bond, -0-, -S- or -NR 1B -, and R 1 is H or lower alkyl and z is an integer from 2 to 4; and R 5 is branched Q-Qoalkylene, phenylene or phenylene substituted by from 1 to 3 methyl groups, benzylene or benzylene substituted by from 1 to 3 methyl groups, cyclohexylene or cyclohexylene substituted by from 1 to 3 methyl groups, cyclohexylene-CH 2 - or cyclo- hexylene-CH - substituted by from 1 to 3 methyl groups. 19. A compound according to claim 1, wherein R j is methyl, allyl, toluylmethyl or benzyl, R 2 is methyl, ethyl, benzyl or phenyl, or R and R 2 togedier are pentametiiylene, R 3 and R are each independendy of die other lower alkyl having up to 4 carbon atoms, or R 3 and R 4 togedier are -CH 2 CH 2 OCH 2 CH 2 -, and R 5 is branched Q-Qoalkylene, phenylene or phenylene substituted by from 1 to 3 methyl groups, benzylene or benzylene substituted by from 1 to 3 methyl groups, cyclohexylene or cyclohexylene substituted by from 1 to 3 methyl groups, cyclohexylene-CH 2 - or cyclo- hexylene-CH 2 - substituted by from 1 to 3 methyl groups. 20. A compound according to claim 1 which is one of the compounds H 2 -0-p-C 6 H 4 -C(0)-C(CH 3 ) 2 -N-moφholiπyl and H 2 ) 2 -0-pC 6 H 4 -C(0)-C(CH 3 ) 2 -N-moφholiπyl 21. A process for the preparation of a compound of formula (I), which comprises reacting a compound of formula II wherein X, Y, R, Rj, R 2 , R 3 and 1^ are as defined hereinbefore, preferably in an inert organic solvent, with a diisocyanate of formula UI or with such a diisocyanate optionally mono-masked OCN-R 5 -NCO (_H), wherein R 5 is as defined hereinbefore. 22. An oligomer or polymer having H-active groups -OH and/or -NH- bonded to die oligo¬ mer or polymer backbone, if desired via a bridge group, or having H-active -NH- groups bonded in die oligomer or polymer backbone, die H atoms of which H-active groups are partly or completely substituted by a radical of formula IV -CONH— R 5 - NH- C - Y - X NR 3 R 4 (TV), wherein R, Rj, R 2 , R 3 , R , R 5 , X and Y have die definitions given hereinbefore. 23. An oligomer or polymer according to claim 22, wherein die oligomer has an average molecular weight of from 300 to 10000 dalton and the polymer has an average molecular weight of approximately from 10000 to 1 000000. 24. An oligomer or polymer according to claim 22, wherein die oligomer or polymer having H-active groups is a natural or syndietic oligomer or polymer. 25. An oligomer or polymer according to claim 24, which is a cyclodextrin, a starch, hyaluronic acid, deacetylated hyaluronic acid, chitosan, trehalose, cellobiose, maltotriose, maltohexaose, chitohexaose, agarose, chitin 50, amylose, a glucane, heparin, xylan, pectin, galactan, poly-galactosamine, a glycosaminoglycane, dextran, aminated dextran, cellulose, a hydroxyalkylcellulose, a carboxyalkylcellulose, fucoidan, chondroitin sulfate, a sulfated polysaccharide, a mucopolysaccharide, gelatin, zein, collagen, albumin, globulin, bilirubin, ovalbumin, keratin, fibronectin or vitronectin, pepsin, trypsin or lysozyme. 26. An oligomer or polymer according to claim 24, which is a hydrolysed polymer of one or more vinyl esters or ethers (polyvinyl alcohol); a hydroxylated polydiolefin, e.g. poly¬ butadiene, polyisoprene or chloroprene; polyacrylic acid or polymediacrylic acid or also a polyacrylate, polymethaciylate, polyacrylamide or polymethacrylamide having hydroxy¬ alkyl or aminoalkyl radicals in the ester group or amide group; a polysiloxane having hydroxyalkyl or aminoalkyl groups; a polyether of one or more epoxides or glycidyl compounds and diols; a polyvinylphenol or a copolymer of vinylphenol and one or more olefinic comonomers; or is a copolymer of at least one monomer from the group vinyl alcohol, vinylpyrrolidone, acrylic acid, methacrylic acid, or a hydroxyalkyl- or aminoalkyl-containing acrylate, methacrylate, or acrylamide or metiiacrylamide, or a hydroxylated diolefin with one or more ethylenically unsaturated comonomers, e.g. acrylonitrile, an olefin, a diolefin, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene, α-methylstyrene, a vinyl ether or a vinyl ester, or is a poly- oxaalkylene having terminal OH or aminoalkyloxy groups. 27. An oligomer or polymer according to claim 24, which is a cyclodextrin having a total of from 6 to 8 glucose structural units forming a ring, or a hydroxyalkyl or amino¬ alkyl derivative or a glucose- or maltose-substituted derivative, of which at least one struc¬ tural unit corresponds to formula (V) wherein R 7 , R 8 and R 9 are each independendy of the otiiers H, Q-Qalkyl, especially methyl, Q-Qacyl, especially acetyl, Q-Qhydroxyalkyl, especially hydroxymethyl or 2-hydroxy- eth-l-yl, Q-Qoaminoalkyl and especially Q-Qaminoalkyl, for example 2-aminoeth-l-yl or 3-aminoprop-l-yl or 4-aminobut-l-yl, Xj is -O- or -NR 1B -, wherein, per cyclodextrin unit, a total of from 1 to 10 and preferably from 1 to 6 radicals Xj may be -NR 1B - and die remaining radicals X j are -O-, wherein R 1B is hydrogen or lower alkyl; and at least one of die radicals R 7 , R 8 and R 9 is a radical of formula (VI) (VI) wherein R, R , R 2 , R 3 , R^J, R 5 , X and Y are as defined hereinbefore, and RJO is a direct bond, -(Q-Qalkylene-O)- or -(Q-Qoalkylene-NH)-, wherein the hetero atom is linked to the carbonyl in formula (VI). 28. An oligomer or polymer according to claim 24, which is an oligomer or polymer that comprises a) from 5 to 100 mol % structural units of formula (VII) and b) from 95 to 0 mol % structural units of formula (VIII) based on die oligomer or polymer, wherein RJJ is Q-Qalkyl, lower alkenyl, cyano-lower alkyl or aryl each unsubstituted or partly or completely substituted by F, and is preferably methyl, etiiyl, vinyl, allyl, cyanopropyl or trifluoromethyl, Rj 2 is Q-Qalkylene, preferably 1,3-propylene, -(CH 2 ) z -(O-CH 2 -CHCH 3 -) z -, -(CH- 2 ) z -(0-CH 2 -CH 2 ) z - or -(CH 2 ) Z -NH-(CH 2 ) Z -NH-, preferably -(CH- 2 ) 3 -(0-CH 2 -CHCH 3 -) 2 - or -(CH 2 ) 3 -NH-(CH 2 ) 2 -NH-, wherein z is independendy of die otiier an integer from 2 to 4, R 14 has the same definitions as RJJ or is -R J2 -XJ-H or -R 1 -Xj-R 5 -H, R 13 is a radical of formula (IX) O O R, -R 15 — CONH Rg- NH- C - Y - X — @- C - C NR 3 R 4 (TX), I R 2 R wherein R, R j , R 2 , R 3 , R 4 , R 5 , X and Y are as defined hereinbefore, and R j5 is a direct bond or a group -C(O)-(CHOH) r -CH 2 -O- wherein r is 0 or an integer from 1 to 4. 29. An oligomer or polymer according to claim 24, which is an oligomeric or polymeric siloxane of formula (X) wherein R is Q-Qalkyl, vinyl, allyl or phenyl each unsubstituted or partly or completely substi¬ tuted by F, and is preferably methyl, R 2 is Q-Qalkylene, preferably 1,3-propylene, R 1 has the same definitions as RJJ or is -R 12 -X j -H or -RJ 2 -XJ-R 15 -H, s is an integer from 1 to 1000 and preferably from 1 to 100, and R 3 is a radical of die above formula (DC) wherein R, Rj, R 2 , R 3 , R , R 5 , X and Y are as defined hereinbefore and Rj 5 is a direct bond or a group -C(O)-(CHOH) r -CH 2 -O- wherein r is 0 or an integer from 1 to 4. 30. An oligomer or polymer according to claim 24, which is an oligomer or polymer that comprises a) from 5 to 100 mol % structural units of formula (XI) and b) from 95 to 0 mol % structural units of formula (XII) wherein R 16 is a radical of the above formula (VI) wherein R, Rj, R 2 , R 3 , R 4 , R 5 , X and Y are as defined hereinbefore and R 10 is a direct bond, -(Q-Qalkylene-O)- or -(Q-Q 0 alkyl- ene-NH)-; R j7 is H, Q-Qalkyl, -COOR 20 or -COO θ , R j8 is H, F, Cl, CN or Q-Qalkyl, and Rjo is H, OH, RJO-H, F, Cl, CN, R 20 -O-, Q-Q 2 alkyl, -COO θ , -COOR 20 , -OCO-R 20 , methylphenyl or phenyl, wherein R 20 is Q-Qgalkyl, C 5 -C 7 cycloalkyl, (Q-Q 2 alkyl)- C 5 -C 7 cycloalkyl, phenyl, (Q-Q 2 alkyl)phenyl, benzyl or (C j -C 12 alkyl)benzyl. 31. An oligomer or polymer according to claim 24, which is an oligomer or polymer that comprises a) from 5 to 100 mol % structural units of formula (XDI) and b) from 95 to 0 mol % structural units of formula (XTV) wherein R 2 ι is H or methyl, X 2 and X 3 arc each independently of the other -O- or -NH-, R 22 is -(CH^ c - and c is an integer from 2 to 12, preferably from 2 to 6, R- 23 is a radical of formula (DC), R j7 and R 18 are as defined hereinbefore, and R- 2 , has the same definitions as Rj or is -C(0)X R 22 X 3 H. 32. An oligomer or polymer according to claim 24, which is a polyoxaalkylene oxide of formula (XV) having identical or different structural repeating units -[CH 2 CH(R 26 )-O]- R 25 — [(CH 2 CH-0-) u ] v — R 2T -X -R n (XV), R26 wherein R- 25 is the group R- 2 g-X 4 - or is the v-valent radical of an alcohol or polyol having from 1 to 20 carbon atoms, R 26 is H, Cj-Cgalkyl, preferably Q-Qalkyl and especially methyl, R 7 together with X 4 is a direct bond or R 27 is Q-Qalkylene, preferably Q-Qalkylene and especially 1,3-propylene, X 4 is -O- or -NH-, R 2 is a radical of formula (IX), u is independendy of die otiier a numerical value from 3 to 10000 and v is an integer from 1 to 6. 33. An oligomer or polymer according to claim 32, which is an oligomer or polymer of formula (XVI) R 25 — [(CF 2 CF-O-)J v — R 27 -X 4 -R 2 g (XVI) Rd wherein R 2 , R 2 g, X , u and v are as defined hereinbefore, R- 25 is as defined hereinbefore or is the monovalent radical of a partly fluorinated or per-fluorinated alcohol having from 1 to 20, preferably from 1 to 12 and especially from 1 to 6 carbon atoms, or the bivalent radical of a partly fluorinated or per-fluorinated diol having from 2 to 6, preferably from 2 to 4 and especially 2 or 3 carbon atoms, and Rj is F or perfluoroalkyl having from 1 to 12, preferably from 1 to 6 and especially from 1 to 4 carbon atoms. 34. A compound of formula (XVII) R-29 — CONH Rg- NH- (XVII) wherein X, Y, R, Rj, R 2 , R 3 , R and R 5 are as defined in claim 1, and R 29 is a vinylic, radically polymerisable hydrocarbon having from 2 to 12 carbon atoms or is a radical of formula (XVIII) wherein R 30 is H or methyl, R 31 is branched or, preferably, linear Q-Q 2 alkylene, lower alkylenearylene or arylene-lower alkylene, or, when w = 0, R 31 may be a bond, w is zero or 1 and X 5 and X 6 are each independendy of die odier -O- or -NH-. 35. A compound of formula (XDC) O R 32 -D r E 2 - D,- R 5 - NHC - Y - NR 3 R 4 (XIX) wherein E 2 is -Xj-(CH 2 ) m -Xj- and each Xj independently of the otiier is -O- or -NH- and m is an integer from 2 to 6, q is zero or 1, Dj is -NHCO-, and 71 R 32 is a radical of formula (XX) wherein X, Y, R, Rj, R 2 , R 3 , I^ and R 5 are as defined in claim 1. 36. A compound of formula (XXI) {R 33 -E 3 -} 3 -T (XXI), wherein R 3 is a compound of formula (XXII) O O R-, — f D 2- R 5^~ NH c ' - Y - --Q - C — C — NR 3 R 4 (xxπ), wherein X, Y, R, Rj, R 2 , R 3 , R 4 and R 5 have die definitions given in claim 1, including the preferred definitions, q is independendy of die other zero or 1, D 2 is -NHCO-, -CONH- or -NHCONH-, E 3 is lower alkylene and T is a trivalent organic or inorganic radical. 37. A radiation-sensitive composition, comprising a) at least one ethylenically unsaturated photo-polymerisable or photo-crosslinkable compound and b) an effective initiator quantity of at least one compound of formula (I), (XVII), (XDC) or (XXI) or of an oligomer or polymer having structural units of formula (IV). 38. A radiation-sensitive composition according to claim 37, wherein a compound of component b) is present in an amount of from 0.001 to 70 % by weight, based on component a). 39. A material consisting of (a) an inorganic or preferably organic substrate to which (b) there is bonded as photoinitiator at least one compound of formula (I), which is firmly bound to die substrate by way of O atoms, S atoms, HN-Q-Qalkyl groups or NH groups, on the one hand, and by die isocyanate group of the photoinitiators, on the other hand, and, optionally, (c) a thin layer of a polymer on the photoinitiator layer, which polymer can be obtained by applying a thin layer of photo-polymerisable ethylenically unsaturated substances to the substrate surface provided widi photoinitiator radicals and polymeri¬ sation of the layer of ethylenically unsaturated substances by irradiation, preferably with UV radiation. 40. A process for modifying surfaces of inorganic or organic substrates that contain H-active HO-, HS-, HN-Q-Qalkyl groups or -NH 2 - groups, comprising the steps of a) applying to the substrate a thin layer of a photoinitiator of at least one compound of formula (I), where appropriate together with a catalyst, b) where appropriate heating the coated material and washing off the excess photoinitiator, c) applying a thin layer of a photo-polymerisable ethylenically unsaturated substance to the substrate surface provided widi said photoinitiator, and d) irradiating the layer containing the ethylenically unsaturated substance preferably with UV radiation. 41. A process according to claim 40, wherein the substrate is a contact lens or an ophthalmic moulded article. 42. A contact lens comprising (a) a transparent organic base material having functional groups, especially hydroxy, mercapto, amino, alkylamino or carboxy groups, and (b) a tiiin layer on the surface, consisting of constituents that are preferably derived from (bl) at least one photoinitiator of formula (I) which is bonded to a functional group of the base material via an isocyanate group, and (b2) a graft polymer formed by photo-copolymeri- sation of an olefin. 43. A contact lens comprising an oligomer or polymer according to claim 22 and a tiiin outer layer on at least a portion of the surface, consisting of a graft polymer formed by photo-polymerisation of an olefin. 44. A contact lens comprising an oligomer or polymer according to any one of claims 23 to 33 and a tiiin outer layer on at least a portion of die surface, consisting of a graft polymer formed by photo-copolymerisation of an olefin. 45. A contact lens comprising (a) a transparent organic base material having functional groups, especially hydroxy, mercapto, amino, alkylamino or carboxy groups, and (b) a tiiin layer on the surface, consisting of constituents that are preferably derived from at least one photoinitiator of formula (I) which is bonded to a functional group of the base material via an isocyanate group. 46. A contact lens comprising an oligomer or polymer according to claim 22. 47. A contact lens comprising an oligomer or polymer according to any one of claims 23 to 33. 48. A polymer obtainable by photo-polymerisation of a composition according to claim 37. 49. A contact lens or ophthalmic moulded article consisting of a polymer according to claim 48.

Inventors: CHABRECEK PETER, DIETLIKER KURT, LOHMANN DIETER, CHABRECEK, PETER, DIETLIKER, KURT, LOHMANN, DIETER
Applicants: CHABRECEK PETER, CIBA GEIGY AG, DIETLIKER KURT, LOHMANN DIETER, CHABRECEK, PETER, CIBA-GEIGY AG, DIETLIKER, KURT, LOHMANN, DIETER
Application year: 1995
Main classification: C07C271
IPC codes: C07C271, C07C323, C07D295, C07F7, C08F2, C08F8, C08F283, C08F290, C08G18, C08G77, C09B69, G02B1, G03F7