CA2127200A1

CA2127200A1 - Functionalized photoinitiators, macromers thereof, and the use thereof

Info

Publication number: CA2127200A1
Application number: CA002127200A
Authority: CA
Inventors: Peter Chabrecek; Dieter Lohmann
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1993-07-02
Filing date: 1994-06-30
Publication date: 1995-01-03
Also published as: DK0632329T3; HK1003846A1; IL110171A; AU6603994A; PL180201B1; CZ161094A3; ATE160888T1; MX9404973A; JP4053612B2; ZA944758B; IL110171A0; HUT69305A; AU683256B2; FI943129A; KR950003265A; EP0632329A1; HU219502B; FI943129A0; NO942495D0; NZ260892A

Abstract

Functionalized photoinitiators, macromers thereof. and the use thereof.
Abstract Compounds of the formula I or Ia (I), (Ia), in which X is O; Y is O, NH or NR6; Y1 is O; Y2 is -O-, -O-(O)C-, -C(O)-O- or -O-C(O)-O-; the n indices, independently of one another, are 0 or 1; R is H, C1-C12alkyl, C1-C12alkoxy or C1-C12alkyl-NH-; the R1 and R2 radicals, independently of one another, are H, linear or branched C1-C8alkyl, C1-C8hydroxyalkyl or C6-C10aryl, or two groups R1-(Y1)n- together are -(CH2)x-, or the R1-(Y1)n- and R2-(Y1)n- groups together form a radical of the formula ;

R3 is a direct bond or linear or branched C1-C8alkylene, which is unsubstituted or substituted by -OH and/or is uninterrupted or interrupted by one or more -O-, -O-C(O)- or -O-C(O)-O- groups; R4 is branched C3-C18alkylene, C6-C10arylene which is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy, C7-C18aralkylene which is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy, C3-C8cycloalkylene which is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy, C3-C8cycloalkylene-CyH2y- which is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy, or -CyH2y-(C3-C8cycloalkylene)-CyH2y- which is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy; each R5, independently of the others, has the same meaning as R4 or is linear C3-C18alkylene; R6 is linear or branched C1-C6alkyl; x is an integer from 3 to 5; y is an integer from 1 to 6; Ra and Rb, independently of one another, are H, C1-C8alkyl, C3-C8cycloalkyl, benzyl or phenyl; with the provisos that n in the -(Y1)n-R1 groups is 0 if R2 is H; that at most two Y1 radicals in the -(Y1)n- groups in the formula I are O and n in the other -(Y1)n- groups is O; that at most one Y1 in the -(Y1)n- groups in the formula Ia is O and n in the other -(Y1)n- group is O; and that n in the -(Y2)n- group is 0 if R3 is a direct bond.

The compounds are photoinitiators which can be functionalized by means of ethylenic groups or can be bonded to H-active substances, in order, for example, to modify surfaces by means of photopolymerizable substances.

Description

2l27,~a~

Functionalized photoinitiators, macromers thereof, and the use thereof.

The present invention relates to hydroxyl-containing acetophenones which have been functionalized by means of organic diisocyanates; to oligomers and polymers to which functionalized acetophenones of this type are bonded; to polymerizable photoinitiators; to ethylenically unsaturated acetophenones linked via a bifunctional diisocyanate linker; to the use of all these acetophenones as photoinitiators; to coated materials; and to the use of functionalized acetophenones for the modification of surfaces.

The compounds of the alkylphenone type or hydroxyalkylphenone type containing the structural unit of the formula (A) ~} C--C-OH (A) are excellent photoinitiators for radiation-induced polymerization of ethylenically unsaturated, monomeric, oligomeric or polymeric compounds. A particular disadvantage in many cases is found to be a discoloration (yellowing) of the polymers formed and the toxic properties of the resultant low-molecular-weight fragments, which can impair the use proJ)erties of the polymers prepared in this way. In order to avoid this disadvantage and other disadvantages of such monomeric photoinitiators, EP-A-0 281 941 proposes modifying photoinitiators on the phenyl ring in such a way that the photolysis products are strongly bonded in the resultant polymer association. Very generally, isocyanate groups are also mentioned as functional groups for this purpose, bonded to the phenyl ring via a spacer group, for example a linear alkylene group. However, the preparation of such compounds causes considerable synthetic problems, since the forrnation of diadducts cannot be avoided, and even predominates, in the reaction of linear diisocyanates with hydroxyl-containing compounds.

There is a demand for functional photoinitiators containing structural units of the formula (A) which are simple to prepare, can be obtained in high purity, are distinguished by high reactivity and a long shelf life and can be adducted onto suitable oligomers or polymers in 7,;': `

." ~ .
j":, .
:
~,,.,: ' :

~,, , ,, ~
, . , 7~a order to prepare macromeric photoinidators of high activity which are suitable for the modification of surfaces, in particular surfaces of plastics, by photoinduced graft polymerization, and can also be used for biocompatible materials, in particular in the biomedical sector, for example for contact lenses. It has been found that this object can be achieved if the introducdon of isocyanate groups is carried out by reacting diisocyanates containing isocyanate groups of different reacdvity with functional groups bonded to the phenyl ring in the formula (A), or reacting the hydroxyl group in the structural unit (A) vith diisocyanates, thus suppressing, through high regioselectivity, the formation of isomers and other byproducts.

The invention relates to compounds of the formula I or la XCN--R4--NHC Y--R3-(Y2)~ C--C -(Y1)nR2 (I), R (Y1)-X (Y~)-R~ O
XCN~ NHC-Y--R31Y2~n C--C~ (Ia), (Y~)-R1 R

in which X is O; Y is O, NH or NR6; Yl is O; Y2 is -O-, -~(O)C-, -C(O)~ or -O-C(O)-O-; the n indiccs, independently of one another, are 0 or l; R is H, Cl-Cl2alkyl, Cl-CI2allcoxy or Cl-Cl2alkyl-NH-; the Rl and R2 radicals, independently of one another, are H, linear or branched Cl-C8aL~cyl, Cl-C8hydroxyalkyl or C6-CIOaryl, or two groups R~-(YI)n- together are -(CH2)X-, or the Rl-(YI)n- and R2-(YI)n- groups together forrn a radical of the formula R R
~ b 0~0 ;
C/

R3 is a direct bond or linear or branched Cl-C8alkylene, which is unsubstituted or substituted by -OH andlor is uninte~upted or interrupted by one or more -O-, -O-C(O)- or 2 ~ 2 5'~

-O-C(O)-O- groups; R4 is branched C3-CI8alkylene, C6-CIOarylene which is unsubstituted or substituted by Cl-C4alkyl or Cl-C4alkoxy, C7-Clgaralkylene which is unsubstituted or substituted by Cl-C~alkyl or Cl-C4alkoxy, C3-C8cycloalkylene which is unsubstituted or substituted by Cl-C4alkyl or Cl-C4aLkoxy, C3-C8cycloalkylene-CyH2y- which is unsubstituted or substituted by Cl-C4alkyl or Cl-C4alkoxy, or -CyH2y-(C3-C8cycloalkylene)-CyH2y- which is unsubstituted or substituted by Cl-C4alkyl or Cl-C4alkoxy; each R5, independently of the others, has the same meaning as R4 or is linear C3-CI8aL~cylene; R6 is linear or branched Cl-C6aL~yl; x is an integer from 3 to 5; y is an integer from 1 to 6; Ra and Rb, independently of one another, are H, Cl-C8alkyl, C3-C8cycloalkyl, benzyl or phenyl; with the provisos that n in the -(YI)n-RI groups is O if R2 is H; that at most two Yl radicals in the -(YI)n- groups in the foTmula I are O and n in the other ~(YI)n~ groups is O; that at most one Yl in the -(YI)n- groups in the formula Ia is O and n in the other -(YI)n- group is O; and that n in the ~(Y2)n~ group is O if R3 is a direct bond.

In a preferred embodiment, Y is 0.

Alkyl R6 can be, for example, methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, pentyl or hexyl. R6 is preferably methyl.

Alkyl, alkoxy or alkyl-NH- R preferably contains l to 6, particularly preferably 1 to 4, carbon atoms. Some examples are medlyl, ethyl, n- and i-propyl, n-, i- and t-bu~l, pentyl, hexyl, octyl, decyl, dodecyl, methoxy, ethoxy, propoxy, butoxy and methyl-NH-. R is particularly preferably H.

Alkyl Rl is pre~erably linear and preferably contains 1 to 4 carbon atoms. Some examples are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, pentyl, hexyl, heptyl and octyl. Rl is particularly preferably methyl or ethyl. Aryl Rl can be, for example, naphthyl, in particular phenyl. If both Rl-(YI)n- groups are -(C~I2),~-, X iS preferably 4, particularly preferably 5. Hydroxyalkyl Rl is preferably linear and p~eferably contains 1 to 4 carbon atoms. Some examples are hydroxymethyl and 2-hydroxy-1-ethyl.

The same preferences apply to R2 as for Rl. R2 is parlicularly preferably H, methyl or ethyl.

Ra and Rb are preferably, independently of one another, H or Cl-C4alkyl, for example ,~ , :

,. . :

2~272~

methyl or ethyl.

In a preferred sub-group, Rl is preferably ethyl, particularly preferably methyl, or both Rl-(YI)n- groups together are pentamethylene, n in the -~YI)n-R2 group is preferably 0, R2 is preferably methyl, hydroxymethyl or H, and R is preferably H.

In another preferred embodiment, Yl in the -(YI)n- R2 group is O, n is 1 and R2 is H. In this case, n in the Rl-(Yl)n- groups is in particular 0.

ALcylene R3 preferably contains 1 to 6, particularly preferably 1 to 4, carbon atoms and the aLkylene is preferably linear. Some examples are methylene, ethylene, 1,2- and 1,3-propylene, 1,2-, 1,3- and 1,4-butylene, pentylene, hexylene, heptylene and octylene.
Preference is given to methylene, ethylene, 1,3-propylene and 1 ,4-butylene. R3 is very pardcularly preferably ethylene or a direct bond, in which case n in the -(Y2)n- group is 0.

Hydroxy-subsdtuted alkylene R3 can in particular be, for example, 2-hydroxy-1,3-propylene or 2-hydroxy-1,3- or 1,4-butylene. Alkylene which is interrupted by -O- and is unsubstituted or substituted by -OH is, for example, -CH2CH2-O-CH2CH2-, -CH2CH2-O-CH2CH2-O-CH2CH2-,-CH2CH2-O-CH2CH2-O-CH2CH2-O-CH2CH2-, [-CH(CH3)CH2-O-CH(CH3)CH2-], -CH(CH3)CH2-O-cH2cH2-~-CH(C2H5)CH2-O-CH2CH2-. [-CH(c2H5)cH2-O-cH(c2Hs)cH2-]~
-CE'~2CH2CH2CHrO-CH2CH2CH2CH2- or -CH2CH(OH)CH2-O-CH2CH2-. Alkylene which is interrupted by -O-C(O)- or -C(O)-O- is, for example, -CH2CH2-C(O)-O-C~2- or -CH2CH2-O-C(O)-CH2-. ALIcylene which is interrupted by -O-C(O)-O- is, for example, -CH2CH2-O-C(O)-O-CH2CH2- or -CH2CH2-O-C(O)-O-CH2-.

The Cl-C4aL~cyl and Cl-C4alkoxy substituents are preferably methyl, ethyl, methoxy or ethoxy.

Branched aLkylene R4 preferably contains 3 to 14, particularly preferably 4 to 10, carbon atoms. Examples of alkylene are 1 ,2-propylene, 2-methyl- and 2,2-dimethyl- 1 ,3-pro-pylene, 1,2-, 1,3- and 2,3-butylene, 2-methyl- and 2,3-dimethyl-1,4-butylene, 1,2-, 1,3-and 1 ,4-pentylene, 2-methyl- and 3-methyl- and 4-rnethyl- and 2,3-dimethyl- and2,Wmethyl and 3,4 dimethyl- and 2,3,4-trimethyl and 2,2,3-trimethyl- 2,2,~trimethyl-and 2,2,3,3-tetramethyl- and 2,2,3,4-tetramethyl-1,5-pentylene, 1,2-, 1,3-, 1,4- and l,S-hexylene, 2-methyl- and 3-methyl and ~methyl- and 2,2-dimethyl- and 3,3~imethyl-, ~,.......... .
"

:
, , .

i :- 21~72~3'~

and 2,3-dimethyl- and 2,4-dimethyl- and 3,4-dimethyl- and 2,2,3-trimethyl- and 2,2,4-trimethyl- and 2,2,5-trimethyl- and 2,3,4-trimethyl- and 2,2,4,5-tetramethyl-1,6-hexylene, 1,2-, 1,3-,1,4- l,S and 1,6-heptylene, 2-methyl- and 3-methyl- and 4-methyl- and S-methyl- and 2,2-dime~yl- and 3,3-dimethyl- and 2,3-dimethyl- and 2,4-dimethyl- and 3,4-dimethyl- and 2,2,3-trimethyl- and 2,2,4-trimethyl- and 2,2,5-trimethyl- and 2,2,6-trimethyl- and 2,3,4-trimethyl- and v 2,4,5-trimethyl- and 2,4,6-trimethyl- and 2,2,4,5-tetramethyl-1,7-heptylene, 1,2-, 1,3-, 1,4-l,S- 1,6- and 1,7-octylene, 2-methyl- and 3-methyl- and 4-methyl- and S-methyl- and 6-methyl- and 7-methyl- and 2,2-dimethyl- and 3,3-dimethyl- and 2,3-dimethyl- and 2,4-dimethyl- and 3,4-dimethyl- and 2,6-dimethyl- and 2,7-dimethyl- and 2,2,4-trimethyl-and 2,2,5-trimethyl- and 2,2,6-trimethyl- and 2,2,5,6-tetramethyl-1,8-octylene, 1,2-, 1,3-, 1,4- l,S- 1,6-, 1,7- and 1,8-nonylene, 2-methyl- and 3-methyl- and 4-methyl- and 5-methyl- and 6-methyl- and 7-methyl- and 8-methyl and 2,2-dimethyl- and 3,3-dimethyl-and 2,3-dimethyl- and 2,4-dimethyl- and 3,4-dimethyl- and 2,6-dimethyl- and 2,7-dimethyl- and 2,8-dimethyl- and 2,2,4-trimethyl- and 2,2,5-trimethyl- and 2,2,6-trimethyl- and 2,2,7-trimethyl- and 2,2,8-trimethyl-nonylene, 1,2-, 1,3-, 1,4- 1,5-1,6-, 1,7-, 1,8- and l,9-decylene, 2-methyl- and 3-methyl- and 4-methyl- and 5-methyl-and 6-methyl- and 7-methyl- and 8-methyl- and 9-methyl- and 2,2-dimethyl- and 3,3-dimethyl- and 2,3-dimethyl- and 2,4-dimethyl- and 3,4-dimethyl- and 2,6-dimethyl-and 2,7-dimethyl-, 2,8-dimethyl- and 2,9-dimethyl-1,10-decylene, 1,2-, 1,3-, 1,4- l,S- 1,~, 1,7-, 1,8-, 1,9- and l,10-undecylene, 2-methyl- and 3-methyl- and 4-methyl- and 5-methyl-and 6-methyl- and 7-methyl- and 8-methyl- and 9-methyl- and 10-methyl-1,11-undecylene, 1,4- l,S- 1,6-,1,7-, 1,8-, 1,9-, 1,10- and l,ll-dodecylene.

Some preferred branched allcylene radicals are 2,2-dimethyl-l,~butylene, 2,2-dirnethyl-l,S-pentylene, 2,2,3- and 2,2,4-trimethyl-l,S-pentylene, 2,2-dimethyl-l,~hexylene, 2,2,3-and 2,2,4- and 2,2,5-trimethyl-l,~hexylene, 2,2-dimethyl-1,7-heptylene, 2,2,3- and 2,2,4-and 2,2,5- and 2,2,6-trimethyl-1,7-heptylene, 2,2-dimethyl-1,8-octylene, 2,2,3- and 2,2,4-and 2,2,5- and 2,2,6- and 2,2,7-trimethyl-1,8-octylene.

Arylene R4 is preferably naphthylene, pa~ticularly preferably phenylene. Any substituents on the arylenee are preferably in the and tho-position to an isocyanate group. Examples of substituted arylene are l-me~hyl-2,4-phenylene, 1,S-dimethyl-2,4-phenylene, l-methoxy-2,~phenylene and 1-methyl-2,7-naphthylene.

Aralkylene R4 is preferably naphthylalkylene, particularly preferably phenylalkylene. The ' - -, ~ , -:.. , ., . ~ - ~ ,.

, . . . .

- ~27~3 aLlcylene group in the aralkylene preferably contains I to 12, particularly preferably 1 to 6, especially preferably 1 to 4, carbon atoms. The alkylene group in the aralkylene is very particularly preferably methylene or ethylene. Some examples are 1,3- and 1 ,4-benzylene, naphth-2-yl-7-methylene, 6-methyl-1,3- and 1,4-benzylene, and ~methoxy-1,3- and 1,4-benzylene.

Cycloalkylene R4 is preferably Cs- and C6cycloalkylene, which is unsubstituted and substituted by methyl. Some examples are 1 ,3-cyclobutylene, 1 ,3-cyclopentylene, 1,3- and 1 ,4-cyclohexylene, 1,3- and 1,4-cycloheptylene, 1,3- and 1,4- and 1 ,5-cyclooctylene, 4-methyl- 1 ,3-cyclopentylene, 4-methyl- 1 ,3-cyclohexylene, 4,4-dimethyl- 1 ,3-cyclohexylene, 3-methyl- and 3,3-dimethyl- 1 ,4-cyclohexylene, 3,5-dimethyl-1,3-cyclohexylene and 2,4-dimethyl-1,4-cyclohexylene.

Cycloallcylene-CyH2y- R4 is preferably cyclopentylene-CyH2y-, particularly preferably cyclohexylene-CyH2j, which is unsubstituted or substituted, preferably by 1 to 3Cl-C4alkyl radicals, particularly preferably by methyl. In the -CyH2y~ group, y is preferably an integer from 1 to 4. The -CyH2y~ group is more preferably ethylene and particularly preferably methylene. Some examples are cyclopent-l-yl-3-methylene,3-methylcyclopent- 1 -yl-3-methylene, 3,4-dimethylcyclopent- 1 -yl-3-methylene, 3,4,4-trimethylcyclopent-1-yl-3-methylene, cyclohex-1-yl-3- and -4-methylene, 3- and 4-and 5-methylcyclohex-1-yl-3- and -4-methylene, and 3,4- and 3,5-dimethylcyclohex-1-yl-3- and -4-methylene, 3,4,5- and 3,4,4- and 3,5,5-trimethylcyclohex-1-yl-3- and-4-methylene.

-CyH2y-cycloaLtcylene-CyH2y- R4 is preferably -CyH2y-cyclopentylene-C~,H2y-, par~icularly preferably -CyH2jcyclohexylene-CyH2y-~ which is unsubstituted or substituted, preferably by 1 to 3 Cl-C4aLkyl radicals, particularly preferably by methyl. In the -CyH2y- group, y is preferably an integer from 1 to 4. The -CyH2y~ group is more preferably ethylene and particularly preferably methylene. Some examples are cyclopentane-1,3-dimethylene, 3-methylcyclopentane-1 ,3~imethylene, 3,4-dimethylcyclopentane- 1 ,3-dimethylene, 3,4,4-trimethylcyclopentane- 1 ,3-dimethylene, cyclohexane- 1,3- and -1 ,4-dimethylene, 3-and 4- and 5-methylcyc10hexane-1,3- and -1,4-dimethylene, 3,4- and 3,5-dimethylcyclohexane-1,3- and -1,4-dimethylene, 394,5- and 3,4,4- and 3,5,5-trimethylcyclohexane- 1,3- and -1 94-dimethylene.

If Rs has the same meaning as R4, the preferences given above for R4 also apply. Linear ~, ~

s,- ~ .

- 2~ 27~f~

alkylene Rs preferably contains 3 to 12, par~cularly preferably 3 to 8, carbon atoms. Some examples of linear alkylene are 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,~hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecy1ene, 1,12-dodecylene~ 1,14-tetradecylene and 1,18-octadecylene.

A preferred sub-group of compounds of the formulae I and Ia comprises those in which n in the Rl-(Yl)n- groups is 0, X, Y, Y2 and Yl in the R2-(YI)n- group are each 0, n in the R2-(YI)n- group is O or 1, Rl is Cl-C4alkyl or phenyl, or the Rl-(Yl)n- groups together are tetramethylene or pentamethylene, R2 is Cl-C4alkyl or H, R is hydrogen, n in the -(Y2)n-group is O or 1, R3 is linear or branched C2-C4alkylene or a direct bond, in which case n in the -(Y2)n- group is 0, R4 is branched Cs-CIOalkylene, phenylene or phenylene which is substituted by 1 to 3 methyl groups, benzylene or benzylene which is substituted by 1 to 3 methyl groups, cyclohexylene or cyclohexylene which is substituted by 1 to 3 methyl groups, cyclohexyl-CyH2y- or -CyH2y-cyclohexyl-CyH2y- or cyclohexyl-CyH2y- or -CyH2y-cyclohexyl-CyH2y-~ each of which is substituted by 1 to 3 methyl groups, Rs is as defined for R4 or is linear C3-ClOalkylene, and y is 1 or 2.

A particularly preferred sub-group of compounds of the formulae I and Ia comprises those in which n in the R~ )-n and -(Y2)n- groups is 0, X, Y, Y2 and Yl in the R2-(YI~n- group are each 0, n in the R2-(Yl)n- group is O or 1, Rl is methyl or phenyl or the Rl~(Yl)n~
groups together are pentarnethylene, R2 is methyl or H, R is hydrogen, n in the -(Y2)-n group is 1 and R3 is ethylene, or n in the -(Y2)n- group is O and R3 is a direct bond, R4 is branched C6-CIOalkylene, phenylene or phenylene which is substituted by 1 to 3 methyl groups, benzylene or benzylene which is substituted by 1 to 3 methyl groups, cyclohexylene or cyclohexylene which is substituted by 1 to 3 methyl groups, cyclohexyl-CH2- or cyclohexyl-CH2- which is substituted by 1 to 3 methyl groups, and Rs is as defincd for R4 or is linear Cs-CIOalkylene.

The R4 and Rs groups are in particular those which reduce the reactivity of the XCN
group, which is essentially achieved by steric hindrance on at least one adjacent carbon atom. R4 and Rs are therefore preferably alkylene which is branched in the a- or in particular the ~-position to the XCN group, or cyclic hydrocarbons which are substituted in at least one a-pOsitiOn as defined.

Some examples of particularly preferred compounds are ~' - ,'' : . ~ . , ~1~7 H3C CH3 :
H3C~CH2-NCO
NH-C(O)-O-CH2CH2-O-p-C6H4-C(O)-C(CH3)2-OH

OCNCH2C(CH3)2CH2CH(CH3)(CH2)2NHC(O)O(CH2)20 ~ C(O)C(CH3)20H

H3C ~CH2-NCO
NH-C(o)-o-c(cH332-c(o)-c6H5 OCNCH2C~CH3)2CH2CH(CH3)(CH2)2NHC(O)-O-C(CI13)2-C(O) H3C ~CH2-NCO : ~ :
NH-C(O)-O~ C(O)-C6H5 OcNcH2c(cH332cH2cH(cH3)(cH2)2NHc(o)-o--C--C(O)-C6Hs - .

~NCO

NH-C(O)-O-(CH2)2-O-pC6H4-C(O)-C(CH3)2-OH

h~NCO
~ .
NH-C(O)-O-C(CH3)2-c(O)-c6H6 :::, . ' - - . - -, ,: , . :
~.,. ~, ~" . , .

21 272~

~NCO

NH-C(O)-O~ C(O)-C6HS

I NCO
1~ f()C6H5 NH-C(O)-OCH--C6H5 The compounds of the formulae I and Ia can be prepared in a manner known per se by reacting diisocyanates with the corresponding H-acidic photoinitiators. The compounds are obtained in high yields and purities, even if the photoinitiator simultaneously contains two H-acidic groups of different reactivity, for example 2 OH groups. It is particularly advantageous to use diisocyanates containing isocyanate groups of different reactivity, since this allows the forrnation of isomers and diadducts to be substantial1y suppressed.
The different reactivity can be achieved, for exarnple, as described above, by steric hindrance. The different reactivity can also be achieved by blocking an isocyanate group in the diisocyanate, for example by means of carboxylic acids or hydroxylamine.

The invention furthermore relates to a process for the preparation of the compounds of the fomlulae I and Ia, which compIises reacting a compound of the forrnula II or IIa H--Y--R3--(Y2)~ C--C ~Y1)-R2 (II), R (Y1)-R

(Y1)-R~
H - Y - R3 (Y2) n I C ~3 (IIa), (Y1)-R1 R

in which Y, Yl, Y2, R, Rl, R2, R3 and n are as defined above, with a diisocyanate of the formula III or IIIa XCN-R4-NCX (III), - ,~, ,, -.. , ~ " : :. : ' ~ ~7~

XCN-Rs-NCX (IIIa), in which R4, Rs and X are as defined above, or an unblocked or monoblocked diisocyanate of this type, in an inert organic solvent, in pardcular at a temperature of up to 40C, preferably at room temperature.

Blocking agents are known from urethane chemistry. They can be, for example, phenols (cresol or xylenol), lactams (~-caprolactam), oximes (acetoxime or benzophenone oxime), H-active methylene compounds (diethyl malonate or ethyl acetoacetate), pyrazoles or benzotriazoles. Blocking agents are described, for example, by Z.W. Wicks, Jr. in Progress in Organic Coatings, 9 (1981), pages 3-28.

The compounds of the formulae II and IIa are known photoinidators of the hydroxyalkylphenone type and are described in the literature [see, for exarnple, H.F.
Gruber, Prog. Polym. Sci, Vol. 17, pages 953 to 1044 (1992), Pergamon Press Ltd.]. The isocyanates are compounds which are well known from polyurethane chemistry.

Suitable inert solvents are aprodc, preferably polar solvents, for example hydrocarbons (petroleum ether, methylcyclohexane, benzene, toluene and xylene), halogenated hydrocarbons (chloroform, methylene chloride, trichloroethane, tetrachloroethane and chlorobenzene), ethers (diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane), ketones (acetone, dibutyl ketGne and methyl isobutyl ketone), carboxylic esters and lactones (ethyl acetate, butyrolactone and valerolactone), alkylated carboxamides (N,N-dimethylacetamide and N-methylpyrrolidone), nitriles (acetonitrile), sulfones and sulfoxides (dimethyl sulfoxide and tetramethylene sulfone). Preference is given to polar solvents.

The reactants are advantageously employed in equimolar amounts. The reaction temperature can be, for example, from 0 to 200C. If catalys~s are used, the temperatures can expediently be in the range from 0 to 50C, preferably at room temperature. Examples of suitable catalysts are rnetal salts, such as alkali metal salts of carboxylic acids, tertiary amines, for example (Cl-C6alkyl)3N (triethylamine and tri-n-butylamine), N-methylpyrrolidine, N-methylmorpholine, N,N-dimethylpiperidine, pyridine and 1,~diazabicyclooctane. Tin salts, especially alkyl tin salts of carboxylic acids, for example dibutyltin dilaurate and tin dioctanoate, have proven particularly effective. If the ~'r~

.~ .

~ ~L t~

compounds of the forrnulae II and IIa contain at least two hydroxyl groups, the reaction is expediently carried out at room temperature for selectivity reasons.

The compounds prepared are isolated and purified by known methods, for example by extraction, crystallization, recrystallization or chromatography. The compounds are obtained in high yields and purities. The yields in non-optimized processes can be greater than 85 % of theory.

The compounds of the formulae I and Ia are highly suitable as photoinitiators for ethylenically unsaturated, free-radical-polymerizable compounds, in paTticular those which additionally contain H-active groups, for example OH-, -COOH, -CONH- or NH-groups. In this case, the photoinitiators are substantially covalently bonded to the polymers formed via the isocyanate group and the photochemical decomposition products (free radical initiators or chain terminators) and effectively prevent any associated impairment of the use properties. The invention furthermore relates to the use of the compounds of the formulae I and Ia as photoinitiators for ethylenically unsaturated, free-radical-polymerizable compounds, in particular those additionally containing H-active groups.

The compounds of the formulae I and Ia are also highly suitable for the preparation of oligomeric or polymeric photoinitiators by reaction with functional oligomers or polymers containing active H atoms, for example OH or NH groups. These macromeric photoinitiators are distinguished by good compatibility and high effectiveness, the photochemical decomposition products, as already stated, being covalently bonded in the polymers formed, for example as chain initiators or terminators, so that a long service life is ensured. A further advantage which should be mentioned is the particular structure of the photopolymers, since the polymer chains grow on the macromeric photoinitiator, giving further advantageous use properties. Thus, the properties desired can be established in a targeted way in the photopolymer through the choice of oligomers or polymers.

The invention furthermore relates to oligomers and polymers containing H-active groups -OH and/or -NH- bonded to the oligomer or polymer backbone, if desired via a bridge group, or containing H-active -NH- groups bonded in the oligomer or polymer backbone, some or all of whose H atoms have been substituted by radicals of the formulae IV and/or IVa ~' t :

2~7~

X 11 (Y1)-R1 -C(X)HN--R4NHC--Y--R3-(Y2)~ C - C -(Y1)nR2 (IV), R (Y1)-R

X (Y1)-Rl o -C(X)HN - Rs--NHC - Y--R3-(Y2) n f c ~ (IVa), (Y1)-R1 R

in which R, Rl, R2, R3, R4, Rs~ X, Y, Yl, Y2 and n are as defined above, bonded to the oligomer or polymer backbone.

The H-active groups are principally -COOH, -OH or -NH- groups.

The oligomers can have a mean molecular weight of from 300 to 10 000 daltons andpreferably contain at least 3, more preferably from 3 to 50, particularly preferably from 5 to 20, structural units. The distinction between oligomers and polymers is, as is known, fluid and cannot be defined precisely. The polyrners can contain &om 50 to 10 000, more preferably from 50 to 5000, structural units and have a mean molecular weight of from 10 000 to 1 000 000, preferably from 10 000 to 5 000 000. The oligomers and polymers can also contain up to 95 mol %, more preferably from S to 90 mol %, of comonomeric structural units without H-active groups, based on the polymer.

The oligomers and polymers containing H-active groups can be natural or synthetic oligomers or polymers.

Examples of natural oligomers and polymers are oligosaccharides and polysaccharides and derivatives 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, glucans, heparin, xylan, pectin, galactan, glycosarninoglycans, dextran, aminated dextran, cellulose, hydroxyalkylcelluloses, carboxyalkylcelluloses, heparin, fucoidan, chondroitin sulfate, sulfated polysaccharides, mucopolysaccharides, gelatin, zein, collagen, albumin, globulin, bilirubin, ovalbumin, kera~ bronectin and vitronectin, pepsin, trypsin and Iysozymes.

: . . -~' .
~, ~, - . .

., .
~ .
~, .

The synthetic oligomers and polymers can be substances containing the -COOH, -OH, -NH2 or -NHR7 groups, where R7 is Cl-C6alkyl. They can be, for example, hydrolysed polymers of vinyl esters or ethers (polyvinyl alcohol), hydroxylated polydiolefins, for example polybutadiene, polyisoprene or chloroprene; polyacrylic acid, polymethacrylic acid and polyacrylates, polymethacrylates, polyacrylamides and polymethacrylamides containing hydroxyalkyl or aminoalkyl radicals in the ester group or amide group;
polysiloxanes containing hydroxyalkyl or aminoalkyl groups; polyethers made fromepoxides or glycidyl compounds and diols; polyvinylphenols or copolymers of vinylphenol and ole~mic comonomers; and copolymers of at least one monomer from the group consisting of vinyl alcohol, vinylpyrrolidone, acrylic acid, methacrylic acid or hydroxyalkyl- or aminoalkyl-containing acrylates, methacrylates or acrylamide ormethacrylamide, or hydroxylated diolefins with ethylenically unsaturated comonomers, for example acrylonitrile, olefins, diolefins, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene, a-methylstyrene, vinyl ethers and vinyl esters; and polyoxaaLkylenes containing terminal OH or aminoalkoxy groups.

Examples of preferred oligomers and polymers are cyclodextrins containing a total of 6 to 8 glucose structural units forming a ring, and hydroxyalkyl and aminoalkyl derivatives and glucose- and maltose-substituted derivatives, of which at least one structural unit conforsns to the formula XVI

RgO ~ (XVI), OR~o in which R8, R9 and Rlo, independently of one another, are H, Cl-C4alkyl, in particular methyl, C2-C6acyl, in particular acetyl, Cl-C4hydroxyalkyl, in particular hydroxymethyl or 2-hydroxy-1-ethyl, C2-CI0aminoalkyl and in particular C2-C4aminoalkyl, for example 2-amino-1-ethyl, 3-aminopropyl or 4-amino-1-butyl, and at least one of the radicals R8, Rg and Rlo is a radical of the formulae V and/or Va -R~ ~-C(X)HN--R4- NHC--Y--R3-(Y2);~ C--C -(Y1)-R2 (V), R (Y~)-R~

: -- ~ , :
,, -7~

X ( I 1)nR1 -R11-C(X3HN-Rs--NHC-Y-R3~Y2)nc C~ (Va), (Y1)-R1 R

in which R, Rl, R2, R3, R4, Rs~ X, Y, Yl, Y2 and n are as defined above, and Rll is a direct bond, -(Cl-C4alkylene-O~- or -(C2-CIOalkylene-NH)-.

In a preferred embodiment, from at least half the glucose units to all 6 to 8 glucose units contain at least one radical of the formula V or Va. The abovementioned preferences apply for R, Rl, R2, R3, R4, R5, X, Y, Yl, Y2 and n. Rll is preferably a direct bond, -CHrO-, -CH2CH2-O-, -CH2CH2-NH- or-CH2CH2CH2-NH-.

Examples of other preferred oligomers and polymers are oligo- and polysiloxanes containing, in the alkyl terminal groups or side chains, OH or NH2 groups whose H atoms have been substituted by a photoinitiator according to the invention. These can be random or block oligomers or block polymers. More preferred oligomers and polyrners are those which contain a) from S to 100 mol % of structural units of the fonnula VI

I--O (VI), Rl3 - X~RI4 .

and b) from 9S to 0 mol % of structural units of the formu1a VIa Sl ~ (VIa) Rls based on the oligomer or polymer, where Rl2 is unsubstituted or partly or fully F-substituted Cl-C4alkyl, vinyl, allyl or phenyl, preferably methyl or trifluoromethyl, Rl3 ,~; - , .
~ .. ..

~` 21 ~ s~

is C2-C6alkylene, preferably 1,3-propylene, Rls is as defined for Rl2 or is -R~3-XI-H or -Rl3-XI-Rl6-H, Xl is -O- or -NH-, and Rl4 is a radical of the formulae VlI or VIIa, -Rl6-C(X)HN--R4 NHC--Y--R3-(Y2)~ C--C -(Y1)-R2 (VII), R (Y~)-Rl X (Y1)-R1 o -R16-C(X)HN - Rs--NHC - Y - R3-(Y2) n f c ~ (VIIa), (Y1)~ R

in which R, Rl, R2, R3, R4, Rs, X, Y, Yl, Y2 and n are as defined above, and Rl6 is a direct bcnd or a -C(O)-(CHOH)r-CH2-O- group, in which r is 0 or an integer from 1 to 4. The abovementioned preferences apply for R, Rl, R2, R3, R4, Rs~ X, Y, Yl, Y2 and n. Xl is preferably -NH-.

Other preferred oligomeric or polymeric siloxanes are those of the fonnula VIII
112 --jl2 --R12 Rl4--X~13--S~O- ~ R13--~RI4 (VI~), Rl2 Rls s R12 where Rl2 is unsubstituted or partly or fully F-subs~tuted Cl-C4aL~yl, vinyl, allyl or phenyl, preferably methyl or trifluoromethyl, R13 is C2-C6alkylene, preferably ~ ::
1,3-propylene, R~s is as defined for Rl2 or is -Rl3-XI-H or -Rl3-X1-Rl6-H, Xl is -O- or -NH-, and Rl4 is a radical of the formulae VII or VIIa, -R16-C(X)HN--R4 NHC--Y--R3-(Y2)~ C--C -(Y1)-R2 (VII), ~p ~

f ~
;,.
:, >

,... ..

7~

X ~Y1)-R1 0 ll I n ll -R16-C(X)HN - Rs--NHC - Y - R3-(Y2) n C C ~ (VIIa), (Y1)-Rl R

in which R, Rl, R2, R3, R4, Rs, X, Y, Yl, Y2 and n are as defined above, and Rl6 is a direct bond or a -C(O)-(CHOH)r-CHrO- group, in which r is 0 or an integer from 1 to 4. The abovementioned preferences apply for R, Rl, R2, R3, R4, Rs, X, Y, Y1, Y2 and n. Xl is preferably -NH-.

Other preferred o1igomers and polymers are those based on oligo- and polyvinyl alcohol in which some or all of the H atoms in the OH groups have been substituted by a radical of the formula V or Va. These can be homopolymers containing -CH2CH(OH)- structuralunits or copolymers containing other univalent or divalent structural units of olefims.

More prefe~Ted are oligomers and polymers which contain a) from S to 100 mol % of structural un1ts of the formula IX

--CH2 Cl H (~X) ORl7 and b) from 95 to 0 mol % of structural units of the formula X

Rlg R19 ~H ~1 (X) : ~

in which Rl7 is a radical of the formula V or Va -R1 1-C(X)HN--R4 NHC--Y--R3~Y2)j~ C--C -(Yl)-R2 (V), R IY1~nR1 f;~ ,.". :. ; '' " ~ . ~ :

s ' ., , :
~: .. . .
,: .: - .~: - ~

` 2~7,`'~a X (Y1)-R1 0 -Rl 1-C(X)HN - R5--NHC - Y - R3-(Y2) n C--C ~ (Va), (Y1)-R1 R

in which R, Rl, R2, R3, R4, R5, X, Y, Yl, Y2 and n are as defined above, and Rll is a direct bond, -(Cl-C4aL~cy1ene-O)- or -(C2-CI0alkylene-NH)-; Rl8 is H, Cl-C6alkyl, -COOR2~ or -cOOe, Rlg is H, F, Cl, CN or Cl-C6alkyl, and R20 is H, OH, Rl l-H, F, Cl, CN, R2l-O-, Cl-CI2aL~cyl, cOOe, -COORIo, -OCO-RIo, methylphenyl or phenyl, where R2l is Cl-CI8aLlcyl, Cs-C7cycloaLlcyl, (Cl-CI2alkyl)-Cs-C7cycloalkyl, phenyl, (Cl-CI2alkyl)phenyl, benzyl or (Cl-CI2alkyl)benzyl.

Rl8 is preferably H. Alkyl Rl8 is preferably methyl or ethyl. If Rl8 is -COOR21, R2l is preferably Cl-CI2aL~cyl, in particular Cl-C6alkyl.

AL~cyl Rl9 is preferably Cl-C4alkyl, for example methyl, ethyl, n-propyl or n-butyl. Rlg is preferably H, Cl or C~-C4alkyl.

If R20 is the R2~-0- group, R2~ is preferably Cl-CI2alkyl, in particular Cl-C6alkyl. Alkyl R20 preferably contains 1 to 6, preferably 1 to 4, carbon atoms. If R20 is the -COOR2~
group, R2, is preferably Cl-CI2aLkyl, in particular Cl-C6alkyl, cyclopentyl or cyclohexyl.
If R20 is the -OCO-R2~ group, R2~ is preferably Cl-Cl2aLkyl, in particular Cl-C6alkyl, phenyl or benzyl.

In a preferred embodiment, Rl8 is H, Rl9 is H, F, Cl, methyl or ethyl, and R20 is H, OH, F, Cl, CN, C~-C4alkyl, Cl-C6alkoxy, Cl-C6hydroxyaL~coxy, -COO-C~-C6aL~cyl, -C)O(C-CI-C6alkyl or phenyl.

Particular preference is given to oligomers and polymers in which Rl8 is H, Rl9 is H or methyl, and R20 is H, OH, CN, methyl, OCH3, O(CH2)tOH or -COOCH3, and t is an integer from 2 to 6.

A further preferred group of oligomers and polymers comprises partially or fillly hydroxyalkylated oligo- or polyacrylates or methacrylates or -acrylamides or -methacrylamides in which the primary hydroxyl group or amino group has been substituted by radicals of the forrnula VII or VIIa. They can contain, for example, from S

~"~

.~, . . .
~' :
~, , ~ ~ ' ~ ~7.'~

to 100 mol % of structural units of the formula XI

~H,~ ~1 (XI), C(O)X2R23X3--R24 and from 95 to 0 mol % of structural units of the formula XII

Rl8 Rlg --CH - --~_ (XII) in which R22 is H or methyl, X2 and X3, independendy of one another, are -O- or -NH-, R23 is -(CH2)C-, and c is an integer from 2 to 12, preferably ~rom 2 to 6, R24 is a radical of the formula VII or VIIa, Rl8 and Rlg are as defined above, and R25 is as defined for R2~ or is -C(O)X2R23X3H. The abovementioned preferences apply for R24, R,g, Rlg and R20. The abovementioned preferences apply for X2 and X3.

Other preferred oligomers and polymers are those made from polyaLlcylene ox~des in whieh some or all of the H atoms of the tenninal -OH or -NH2 groups have been substituted by radicals of the formula VII or VIIa These can be, for exa nple, those of the formula xm containing identical or different recurring structural units -[CH2CEI(R27)~]-, R2~, L(CH2CI H-O-)u]~R28~X4~R2g (xm), in which R26 is the R29-X4- group or the v-valent radical of an alcohol or polyol having 1 to 20 carbon atoms, R27 is H, Cl-C8aLIcyl, preferably Cl-C4alkyl, particularly preferably methyl, R28 together with X4 is a direct bond or R28 is C2-C6alkylene, preferably C3-C6alkylene, particularly preferably 1,3-propylene, X4 is ~- or -NH-, R29 is a radical of the formula V~ or VIIa, u has a numerical value of from 3 to 10 000, preferably from 5 to 5000, particularly preferably from 5 to 1000, especially preferably from 5 to 100, and v is ~',.: . ,. ~
. .
"., ~ :
,, ~ , ' , . .

~'' ' J ~ V? '~ ~

an integer from 1 to 6, preferably from 1 to 4.

R26 can be the monovalent to tetravalent radical of an alcohol or polyol. If R26 is the radical of an alcohol, R26 is preferably linear or branched C3-C20alkyl or -alkenyl, C3-C8-, particularly Cs-C6cycloalkyl, -CHr(Cs-C6cycloalkyl), C6-CIOaryl, in particular phenyl or naphthyl, or C7-CI6aralkyl, in particular benzyl or 1-phenyl-2-ethyl. The cyclic or aromatic radicals may be substituted by Cl-Cl8alkyl or Cl-CI8alkoxy.

If R26 is the radical of a diol, R26 is preferably branched and in particular linear C3-C20alkylene or -alkenylene and more preferably C3-CI2alkylene, C3-C8-, in particular Cs-C6cycloalkylene, -CH2-(Cs-C6cycloalkyl)-, -CH2-(Cs-C6cycloalkyl)-CH2-, C7-CI6aralkylene, in par~icular benzylene, -CH2-(C6-CIOaryl)-CH2-, in particular xylylene.
Cyclic or aromatic radicals mày be substituted by Cl-CI2alkyl or Cl-CI2alkoxy.

If R26 is a trivalent radical, it is derived from an aliphatic or aromatic triol. R26 is preferably a trivalent aliphatic radical having 3 to 12 carbon atoms derived, in particular, from a triol, preferably containing primary hydroxyl groups. R26 is particularly preferably -~H2(CH-)CH2-, HC(CH2-)3 or CH3C(CH2-)3.
If R26 is a tetravalent radical, it is preferably derived from an aliphatic triol. In this case R26 is preferably C(CH2-)4.

The abovementioned preferences apply for R29. Particular preference is given to homooligomers and homopolymers and block oligomers and polymers containing structural units of the formulae -[CH2CH2-O~- and -[CH2CH(CH3)-O-]-.

Also suitable are fluorinated polyethers which conform to the formula XIIIa R26--[(CF2CI F--)u]v--R28--X4 R29 (XIIIa~
Rd in which R28, R29, X4, U and v are as defined above, R26 is as defined above or is the monovalent radical of a partially or perfluorinated alcohol having 1 to 20, in particular 1 to 12, particularly preferably 1 to 6, carbon atoms, or the divalent radical of a partially or perfluorinated diol having 2 to 6, preferably 2 to 4, particularly preferably 2 or 3, carbon atoms, and Rd is F or perfluoroalkyl having 1 to 12, preferably 1 to 6, particularly preferably 1 to 4, carbon atoms. Rd is particularly preferably -CF3.

,., . . : , ~;
~'~ '' ' '' ' ' -, ,. . ~ . .

Examples of other suitable oligomers and polymers are polyethyleneimines in which H
a~oms of the NH groups are substituted by radicals of the formulae V and/or Va, including the abovementioned preferences. Poly-~-lysine is likewise suitable.

The oligomers and polymers according to the invention can be prepared in a simple manner known per se by reacting compounds of the formulae I and Ia with HO- or NH-functional oligomers and polymers. NH-functional oligomers and polymers are known in large number and are commercially available; their reaction with sugar acids gives the corresponding esters and amides containing a terminal polyhydroxyalkyl radical.

The photoinitiators of the formulae I and Ia according to the invention can also be used for the preparation of polymerizable photoinitiators containing ethylenically unsaturated groups by reacting the compounds of the formula I or Ia with OH- or NH-functional ethylenica11y unsaturated compounds. This reaction is known to the person skilled in the art and is not described in greater detail. Examples of OH- and NH-functional ethylenically unsaturated compounds are (hydroxyalkyl)- and (aminoalkyl)acrylic and -methacrylic esters and arnides.

The invention furthermore relates to compounds of the formulae XIV and XIVa R30-C(X)HN--R4--NllC--Y--R3-(Y2)~ C - C ~(Yl )nR2 (XIV), R (Y1)-Rl X (Y1)-R1 0 R90-C(X)HN - Rs--NHC - Y - R3-(Y2) n C 8 ~ (XIVa), (Y1)nR1 R
in which X, Y, Yl, Y2, R, Rl, R2, R3, R4, Rs and n are as defined above, including the preferences, and R30 is a radical of the formula XV

CH2 C--C X, R32--Xo (XV) .

.. . . :

r~

in which R3l is H or methyl, R32 is branched or preferal~ly linear C2-Cl2alkylene, and X5 and X6, independently of one another, are -O- or -NH-.

R32 is preferably C2-C6alkylene, for example ethylene, 1,3-propylene, 1,4-butylene, l,S-pentylene or 1,3-hexylene.

Some examples are:

~2=C(cH3)-co-o~2cH2o-co NH~

fH3 y HO-f CO-p-C6H4-O-CH2CH2-O-CO- NH

CH2=C(CH3)-CO-OCH2CH20-CO-NH-C~CH3 CH3 y HO-f-CO-p-C6H4-0-CH2CH2-0-CO- NH

.. , ~ , .
. - -, . , - ~ ~ ' ,. --, ~ , C312=C(CH3)-CO-NH-CH~<CH3 "

CH3 ~/ ' HO-CI -CO-p-C6H4-O-CH2CH2-O-CO- NH

ÇH3 CH2=CH-CO-O-CH2CH(C~13)0-CO-NH-CH~C~3 1CH3 y Ho-f CO-p-C6H4-0-~2CH2-O-CO- NH

The compounds of the formulae I, Ia, XIV and XIVa are highly sui~ble as inidators for radi~don-induced polymerizadon of cthylenically unsaturated compounds. In their specificadon, the compounds of the formulae XIV and ~IVa a~e inco~pora~ed either as a whole or as fragments into the polyrners, cithe~ via the unsaturated group and/or via the f~radicals formed. The oligomers and polyrners accor~ing to the invention are li.kewise highly suitable as inidato~s, in which case graft poly ners are fonned or alternatively, depending on the content of initiator groups in the rnacroinitiator, pcnetratdng polymer networks or those which are only bonded to one another to a panial extent, or not at all, can be forrned.

The invention furthermore relates to a radiation-sensitive composition comprising a) an ethylenically unsaturated, photopolymerizable or photocrosslinlcable compound (referred to as radiadon-sensitive organic material below) and b) an amount, effectdve as inidator, of at least one compound of the formula I, Ia, XIV or XIVa or of an oligomer or polymer containing structural units of the formulae IV and IVa . - .~ . . . . . . .
~, ~ . , . ~ .. . .. . .
~ ";
. , ;,;-, . ~ " :
~:,, - : -, . , :
Sj' ' ~ ' ., ' : , C~ r1 ~ ,rl The compounds of component b) can be present in an amount of from 0.001 to 70 % by weight, in particular from 0.001 to 50 % by weight, especially firom 0.01 to 40 % by weight, very particularly from 0.01 to 20 % by weight, based on component a). The amount depends principally on the photoactive groups bonded in the initiator; the fewer tha~ are present, the larger the added amount selected.

Ethylenically unsaturated, photocrosslinkable compounds and thus also photostructurable 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 non-volatile or low-volatility, monomeric, oligomeric or polymeric substance containing photopo1ymerizable, ethylenica11y unsaturated groups.

Examples of photopolymerizable substances are acrylic and in particular methacrylic esters of alcohols and polyols, and acrylamides and in particular methacrylamides of amines and polya nines, for example Cl-CI8allcanols, ethylene glycol, propanediol, butanediol, hexanediol, di(hydroxymethyl)cyclohexane, polyoxyaLkylenediols, for examplc di-, tri- or tetraethylene glycol, di- and tri-1,2-propylene glycol, tnmethylolmethane, -ethane and -propane, and pentaeryth}itol, Cl-C~8aLkylamines,ethylenediamine, diethylenetriamine and triethylenetetramine, which can be used alone, in mixtures or in blends with binders. Also suitable are mono-, oligo- and polysiloxanes with acrylic and particularly methacrylic esters bonded to pendant or terminal hydroxy(C2-C12aLlcyl) or amino(C2-CI2alkyl)groups, for example l-trimethylsilyl-3-methacroyloxypropane, l-pentamethyldisiloxanyl-3-methacryloxypropane and 3-[tris(trimethylsiloxy)silyl]propyl methacrylate. Also suitable are perfluoroalkyl acryla~es and methacrylates.

The photopolymerizable substances can contain further additives which are conventional for p~ocessing or use, and in addition other photoinitiators or photosensidzers.
The photopolymerizadon is carried out with exposure to radiation, preferably UV
radiation, where known radiation sources can be employed, for example mercury vapour lamps.

, , , ii, ~, ~ ~7~

The compounds of the formulae I and Ia can also be bonded to surfaces of inorganic and organic materials (referred to as substrates below) which contain H-active -COOH, -OH, -SH or -NH- groups. Suitable processes for this purpose are known, for example dipping, spraying, spreading, knife coating, pouring, rolling and in particular spin coating or vacuum vapour deposition processes. The compounds of the formulae I and Ia are firmly anchored to the surface by reaction with the isocyanate groups. This reaction can be carried out, for example, at elevated temperatures, for example at from 40 to 100C. After the reaction, excess compounds can be removed, for example using solvents.
Photopolymerizable substances can then be applied to the modified surfaces and subsequently polymerized by exposure to radiation and firmly bonded to the substrate by graft polymerization via the photoinitiators. In this case, a tentacle-like or brush-like polymer structure forms on the substrate surface.

Examples of suitable substrates are glasses, silicate minerals (silica gels), metal oxides and in particular natural or synthetic polymers, which are known in large number. Some examples of polymers are polyaddition and polycondensation polymers (polyurethanes, epoxy resins, polyethers, polyesters, polyamides and polyimides); vinyl polymers(polyacrylates, polymethacrylates, polystyrene, polyethylene and halogenated derivatives thereof, polyvinyl acetate and polyacrylonitrile); elastomers (silicones, polybutadiene and polyisoprene); modified or unmodified biopolymers (collagen, cellulose, chitosan and the abovementioned biopolymers). If substrates contain too few or no functional ~oups, the substrate surface can be modified by methods known per se, for example plasma methods, and functional groups such as -OH, -NH2 or -CO2H produced. Particularly preferred substrates are contact lenses.

The invention furthermore relates to a material comprising (a) an inorganic or preferably organic substrate to which is bonded (b), as photoinitiator, at least one compound of the formula I or Ia, which is strongly bonded to the substrate via O atoms, S atoms,N-CI-C6alkyl groups or NH groups on the one hand and the isocyanate group of thephotoinitiators on the other hand, and, if desired, (c) a thin coating of a polymer on the photoinitiator layer, this polymer being obtainable by applying a thin coa~ng ofphotopolymerizable, ethylenically unsaturated substances to the substrate surface provided with photoinitiator radicals, and polymerizing the coating of ethylenically unsaturated substances by irradiation, preferably with UV radiation.

.
.. .
., ~ . -.

.: .
~ . .
,,. ~ . . .
, 21 ~ J!

This material is preferably an ophthalmic moulding made from a transparent organic base material, for example a contact lens or an intraocular lens, particularly preferably a contact lens.

The coating thickness of the ethylenically unsaturated substances depends principally on the desired properties. It can be from 0.001 ~m to 1000 llm, preferably from 0.01 ~Im to 500 llm, particularly preferably from 0.01 to 100 ,um, especially preferably from 0.5 to 50 llm, very particularly preferably from 1 to 20 ~,~m. For the production of contact lenses in particular, a coating thickness of from 0.5 to 5 ~,lm is desired. The coating can be produced by the abovementioned coating methods.

The ethy1enica11y unsaturated substances can be the abovementioned compounds. Other suitable ethylenically unsaturated compounds are non-volatile substituted polyolefins, in particular acrylic acid and methacrylic acid, and esters and amides the~eof, for example Cl-Cl2a1kyl or oligooxaalkylene or Cl-CI2hydroxya1kyl acrylates or methacrylates or acrylamides or methacry1amides (2,3-dihydroxypropyl methacrylate, N,N-dimcthylacrylamide, acrylamide, N,N-diethylaminoethyl methacrylate, oligoethylene oxide acrylates and methacrylates, 2-hydroxyethylmethacrylic esters), and N-vinylpyrrolidone.

The invention furthermore relates to a process for modifying surfaces of inorganic or organic substrates containing H-active HO-, HS-, HN-CI-C6a1kyl or -NH2 groups, comprising the steps a) app1ication of a thin coating of photoinitiators of at least one compound of the formulae I and Ia to the substrate, if desired together with a catalyst, for example dibutyltin laurate, b) if necessary warming the coated materia1 and washing off the excess photoinitiator, c) app1ication of a thin coating of photopo1ymerizable, ethylenica11y unsaturated substances to the substrate surface provided with photoinitiator radicals, and d) po1ymerization of the coating of ethylenically unsaturated substances by irradiation, preferab1y with UV radiation.

Any non-covalently bonded polymers formed can be removed after the polymerization, for examp1e by treatrnent with suitable solvents.

The process according to the invention can be used to modify the surfaces in a variety of ways and to provide the surfaces with particular properties for various applications.

~" .
,' ~ , " 2 u l Depending on the choice of the ethylenically unsaturated substances, it is possible, for example, specifically to improve mechanical properties, for example the surface hardness, scratch resistance, wettability, abrasion resistance and writability, and physical properties, for example the coefficient of friction, the permeability to gases, liquids and dissolved inorganic or organic substances of low to high molecular weight, and the opticaltransparency9 particularly strong adhesion of the polymer coatings being a particular advantage.

The photoinitiators according to the invention and the substrates modified by means of the photoinitiators are distinguished by high chemical and photochemical reactivity. They can be used to produce photoreactive materials, which can be used as coating materials, photostructurable materials, for composite materials and in particular as materials for biomedical applications, for example contact lenses and surgical materials. The materials are particularly suitable for the production of hydrophilic and biocompatible surfaces on contact lenses by graft polymerization with formation of a tentacle structure (brush structure) which is particularly suitable for the required properties.

Of particular importance are the high wettability and the fact that a stable moisture film is obtained on the surface, for example a tear film on the surface of a contact lens.
Furthermore, the improvement in the behaviour in biological systems is of considerable importance, for example improved biocompatibility, protection against bioerosion, prevention of plaque formation and of biofouling, and no blood coagulation or toxic or allergic reactions.

The modified rnaterials according to the invention are particularly suitable for the production of contact lenses. With respect to contact lenses, the following property improvements are particularly important: high wettability (small contact angle), high tear -strength, good lubrication effect, high abrasion resistance, only insignificant enzymatic degradation, or none at all, no deposition of components from the tear fluid (proteins, lipids, salts and cell degradation products), no affinity to cosmetics, volatile chemicals, for example solvents, dirt and dust, and no attachment or lodging of microorganisms.
The modified materials according to the invention are also suitable for the production of artificial blood vessels and other biomedical materials for prostheses, for surgery and for diagnostics, where it is particularly advantageous that endothelial cells can grow over them.

' ' ' , .

--i 2~ ~7~

The invention furthermore relates to a contact lens comprising (a) a transparent, organic base material containing functional groups, in particular hydroxyl, mercapto, amino, alkylamino or carboxyl groups, and (b) a thin surface coating comprising (bl) at least one photoinitiator of the formula I or Ia and (b2) a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

Examples of suitable base materials are modified or unmodified natural polymers, for example collagen, chitosan, hyaluronic acid and cellulose esters, such as cellulose acetate or cellulose butyrate, modified or unmodified synthetic polymers, for example polyvinyl alcohol, polyhydroxyethyl methacrylate, polyglyceryl methacrylate, and copolymers based on these polymers. Also suitable are natural and synthetic polymers, for exarnple polymers containing silicone, perfluoroalkyl and/or alkyl acrylate structural units, in which functional groups can be produced on the surface by means of suitable methods, for example plasma treatment, etching or oxidation.

Examples of suitable non-volatile or low-volatility olefins are acrylamide, N,N-dimethylacrylamide, methacrylamide, hydroxyethyl methacrylate, glyceryl methacrylate, oligoethylene oxide mono- and bisacrylates, ethylene glycol dimethacrylate, methylenebisacrylamide, vinylcaprolactam, acrylic acid, methacrylic acid, monovinyl fumarate, vinyl trifluoroacetate and vinylene carbonate.

The examples below illustrate the invention in greater detail.

A) Preparation examPles ExamDle Al: Preparation of H3C~<CH2-NCO
NH-C(O)-O-CH2CH2-O-p-C6H4-C(O)-C(CH3)2-OH

In a 500 ml flask fitted with reflux condenser, thermometer, stirrer and nitrogen inlet tube, a solution of 11.125 g (0.05 mol) of freshly distilled isophorone diisocyanate (IPDI) in 50 ml of dry methylene chloride is mixed under nitrogen with a solution of 11.2 g ... ~ : - ~

~.. , ~ . .

r- 2~.~7~

(0.05 mol) of 4'-(,B-hydroxyethoxy)-2-hydroxyprop-2-ylphenone (Darocure 2959@)) in 300 ml of dry methylene chloride, 20 mg of dibutyltin dilaurate are added as catalyst, and the mixture is stirred at room temperature for 48 hours. The course of the reaction is monitored by thin-layer chromatography on silica-gel plates (6() F2s4, Art. 5719, Merck) (mobile phase: toluene/acetonitrile 7:3). The product obtained is freed from small amounts of unreacted Darocure 2959 and disubstituted IPDI by column chromatography on silica gel 60 (eluent toluene/acetonitrile 7:3). The pure fractions are evaporated on a rotary evaporator, giving a colourless oil, which c~ystallizes slowly on cooling to -16C and is subsequently recrystallized from dry diethyl ether, giving 15.6 g of a white crystalline product (70 % of theory), which has a melting point of 76C.

The isocyanate content of the product is deterrnined by titration with dibutylamine in toluene: calculated 2.242 meq/g, found 2.25 meq/g.

The method is described in "Analytical Chemistry of Polyurethanes" (High PolymerSeries XVI/Part III, D.S. David + H.B. Staley, editors, Interscience Publishers, New York, 1969, p. 86).

Example A2: Preparation of OCNCH2C(CH3)2CH2CH(~H3)(CH2)2NHC(O)O(CH2)20 ~ C(O)C(CH3)20H
Analogously to Pxample Al, 10.5 g (0.05 mol) of 1,6-diisocyanato-2,2,4-trimethylhexane (T~ e reacted with 11.1 g (0.05 mol) of Darocure 2959~ in 400 ml of dry methylene chloride at room temperature under nitrogen for 40 hours. 14.5 g (67 % of theory) of a white, crystalline product having a melting point of 41-43C are obtained. NCO titration:
calculated 2.30 meq/g, found 2.36 meq/g.

Exam~le A3: Preparation of ~3C CH3 H3C ~< CH2-NCO
NH-c(o)-o-c(cH3)2-c(o)-c6H5 Analogously to Example Al, 11.125 g (0.05 mol) of IPDI in 15 ml of dry methylenechloride are reacted with 8.2 g (0.05 mol) of 2-hydroxyprop-2-ylphenone (Darocure ,:. ,:
.
. .

.; , .
.,., ~ ~
:., 2 ~

1173(~)). The reaction mixture is first stirred at room temperature for 24 hours and subsequently heated at 30C for 24 hours and at 45C for 48 hours. After the solvent has been evaporated, the product is purified by chromatography on silica gel 60 using toluene/acetone 7:1 as eluent, giving 12.5 g (70 % of theory) of a white, crystalline product which has a melting point of 100-102C.

NC0 titration: calculated 2.58 meq/g, found 2.52 meq/g.

Examples A4-A6: Analogously to Example A3, further photoinitiators are reacted with diisocyanates in 250 ml of CH2Cl2. The results are shown in Table 1. IRGACURE 184~9 is l-hydroxycyc10hex-l-ylphenone.

, ,, -,.. ,; , . ~ , ...................................... .

, .

Table 1:

Ex- Isocyanate Photo- Yield Melting OCN ti~ation ample initiator point (C) [meq/g]

A4 TMDI Darocure 12.5 g colourless Calculated 2.67 lO.Sg 1173~ [67%of oil Found 2.S2 (0.05 mol) 8.2 g theory]
(0.05 mol) AS IPDI lrgacure 17.5 g 121-123 Calculated 2.34 11.125 g 184 ~g) [82% of Found 2.30 (0.05 mol) 10.25 g theory]
(0.05 mol) A6 TMDI ~gacure 14.1 g colou~ess Calculated 2.41 10.5 g 184~) ~68% of oil Found2.27 (0.05 mol) 10.25 g theory]
(0.05 mol) A4= OcNcH2c(cH3)2cH2cHtcH3)(cH2)2NHc(o)4-c(cH

H3C ~CH2-NCO
A5 = NH-C(O)-O-~C(o)-c6H5 A6 = 0CNCH2C(CH3)2CH2CH(CH3)(CH2)2NHC(O)-O ~ C(O)-C6H5 :-. .::
';'' ' ' ~ :
.~,i:

~,,, 2~ ~7~

Example A7: Preparation of ~NCO

NH-c~o)-o-(cH2)2-o-~c6H4-c(o)-c(cH3)2-oH

In the apparatus described in Example Al,1.74 g (0.01 mol) of tolylene 2,4-diisocyanate (TDI) in 20 ml of dichloromethane are reacted with 2.24 g (0.01 mol) of Darocure 2959~9 dissolved in 60 ml of dry dichloromethane. The reaction mixture, without addidon of a catalyst, is sdrred at room temperature for 48 hours and at 40C for 1 hour until unreacted Darocure 2959 can no longer be detected in the thin-layer chromatogram. The product is isolated by precipitadon of the reacdon solution in 180 mol of dry petroleum ether (b.p.
40-60C) and is subsequently recrystallized twice from dichloromethane/petroleum ether 1:3.

A white, crystalline product of meldng point 124-125C is obtained. Yield 17.2 g, corresponding to 87 % of theory. OCN dtradon: calculated 2.50 meq/g, found 2.39 meq/g.

ExamPles A8-A10:

Analogously to Example A7, tolylene diisocyanate is reacted with various photoinitiators in 40 ml of petroleum ether. The results are shown in Table 2.

s,,: . :
'..,~ ., ., .
f"

- 2 ~

Table 2:

Ex- Isocyanate Photo- Yield Melting OCN ti~ation ample ini~iator point (C) [meq/g]

A8 TDI Darocure 2.8 g 177-178 Calculated 2.95 2.61g 1173~) (83%of Found 2.95 (0.015 mol) 1.6 g theo~y) (0.01 mol) A9 TDI Irgacure 3.33 g 225-226 Calculated 2.64 2.61 g 184 (88% of Found 2.59 (0.015 mol) 2.0 g theory) (0.01 mol~

A10 TDI Benzoin 3.73 g 229-232 Calcu1ated 2.59 2.61 g 2.12 g (79% of Found 2.95 (0.015 mol) (0.01 mol) theory) A8 = 1~

NH-C~O)-O-C(CH3)2-C(O)-C6Hs A9= ~
NH-C(O)-O~ C(O)-C6Hs CH~
I NCO
A10 = 1~ C(O)C6H5 NH-C(O)-O--CH--C6H5 , ~ :
`

, B) Preparation of macrophotoinitiators Example B 1: Preparation of CH3 Cl H3 CH3 (CH3)3Sj O--(Si-O)-a-(Si-O) b (S1 0)-C--Si(CH3)3 CH3 (CH2)3 CH3 NH

Hg CH3 ~2C>[~CH3 IH--C--O--CH2--CHz--O ~ C--C--OH

In a 250 ml flask as described in Example Al, a solution of 1 g of the compound of ~xample Al (Q.QQ224 mol) in 50 ml of dry dich10romethane is reacted with 4.37 g of aminoaLlcylpolysiloxane (0.515 meq of NH2/g, Petrarch PS 813~): Mn - 3000, b = 3, a+c = 37) dissolved in lQO ml of dry dichloromethane. The reaction mixture is stirred at room temperah~re for 10 hours and subsequently warmed at 40C for 1 hour. After the mixture has been cooled, the solvent is removed by evaporation on a rotary evaporator, giving a highly viscous, colourless oil, which is finally freed from traces of dle solvent in a high vacuum at 40C and 104 mmHg. Yield 5.34 g, corresponding to ~9.5 % of theory. The product no longer shows an OCN band in the IR spectrum.

Examples B2-B6: Analogously to Example Bl, further amin~funcdonal macromers are reacted with the compound described in Example Al. The results are shown in Table 3.

.... .
~' ~

~;:
,, 2 ~

Table 3:

Ex- Aminofunctional Compound Structure Yield % N
ample macromer of (Product) (Calculated/
Ex. Al found) B2 X-22-161c 1.5 g a 9.2 g l.5V1.42 (Shin Etsu. JP) ~3.36 mmol) ~99.6%) 7.8 g (0.43 meq NH2/g) M ~ 4600 B3 Jeffamin~ T 403 2.84 g b 5.62g 7.08n.11 (Texaco, USA) (6.36 mmol) (99.7%) 2.8 g (6.38 meq NH2/g) B4 Jeffamin~9 D20C0 1.786 g c 5.78g 2.90/2.89 (Texaco, USA (2.0 mmol) (99.9%) 4.0 g (1 meq NH2/g) B5 KF-8003 1.0 g d 4.55g 1.63/1.58 (Skin Etsu, lP) (2.29 mmol) (98.9%) 4.6 g (0.49 meq NH~/g) B6 X-22-161B 1.0 g e 4.2g 2.23/2.09 (Shin Etsu, JP) (2.29 mmol) (99.3%) 3.23 g (0.699 meq NH2/g) M~ 2900 a= Z -NH--(CH2)3-S~--(O-Si) 6(CH2)3 NH Z

. . - : ., :
! - ::

- -;. -. - - .

2~ ~7~a (O--CH2--CH)-x--NH- Z
b = H3C--CHzC~ (OCH2-CH) y NH--Z

x+y+z = 5-6(O--CH2--CH)--z NH- Z

c = Z--NH CH--CH2--(C--CH2--CH--)--NH--Z

CH3 ~ fH3 CH3 fH3 d = H3C ~ o _ - Si O - _--Si a _--si-- CH3 CH3 - CH3 x (fH2)3 y 7CH3 NH
x:y 27:1 CH3 ~ CH3 Z--NH--(Cl-i2)~ - Si--O~ Si (CH21~ NH--Z

Mc ~ I

z_ HO--C--C ~O--CH2--CH2- O--C--NH~Me Exasnple B7: P eparation of t 2 $ ) a ( CH2--CH )~

a:b z 30:1 n ~ 10 " ~

.,., : , ~, , r :, ~27~n~a In the apparatus described in Example Al, 2.1 g of polyvinyl alcohol (PVA) (Serva~
03/20 Mn ~ 13 000) are dissolved under nitrogen in 50 ml of dry N-methyl-2-pyrrolidone (NMP) at 90C. The solution is cooled to room temperature and ~lltered through a G4 glass frit, and the solution of 0.7 g (1.567 mmol) of the compound of Example Al in 10 ml of dry NMP is added. 10 mg of dibutyltin dilaurate are added, and the reaction mixture is stirred at 50C for 48 hours. After this reaction time, IR spectroscopy shows no evidence of unreacted diisocyanate (OCN at 2280 cm~l). After the mixture has been cooled to room temperature, the product is precipitated in 400 ml of dry diethyl ether, filtered off, washed with dry diethyl ether and dried in vacuo, giving 2.6 g of a white product containing 1.38 % of nitrogen. lH chemical shifts of aromatic protons of the photoinitiators bonded to PVA: ~ 7.00-7.10 (d, 2H); ~ 8.15-8.25 (d, 2H).

Example B8: Reaction of hyaluronic acid with the reactive photoinitiator from Example Al.

Analogously to Example B7, 444 mg of hyaluronic acid (Denki Kagaku Kogyo, Mn ~
1.2xlQ6), disso1ved in 100 ml of dry dimethyl sulfoxide (DMSO), are reacted at 50C with a solution of 200 mg of the compound described in Example 1 in 10 ml of dry DMSO, giving 534 mg (82.7 % of theory) of a white product which carries a photoinitiator group bonded as urethane or carboxamide on about 30 % of the sugar radicals in the main polymer chain, as shown by evaluation of the IH-NMR spectrum. lH chemical shifts of aromatic protons of the photoinitiators bonded to hyaluronic acid: ~ 7.00-7.10 (d,2H);
8.15-8.25 (d, 2H).

Examples B9-B 11: Analogously to Example B8, the reactive photoinitiator described in Example Al is reacted with some hydroxyalkyl-substituted polydimethylsiloxanes in dichloromethane as solvent. The results are shown in Table 4.

.*, ~
,, ~ . , --2~ ~72~a Table 4: -Ex- Photoinidator Poly- Yield E1emental ample fromEx. 1 siloxane analysis % calculated/
found B9 1.0 g KF-6002 4.55 g C 39.87/39.86 (2.25 mmol) (Shin E~su, JP) (98.9%) H 7.96/
8.29 3.6g (0.625 meq O~Vg) N 1.36/1.04 B10 1.0 g KF-6001 3.0 g C 23.49/24.11 (2.23 mmol) (Shin Etsu, ~P) (98.3%) H 8.12J
8.54 2.05g (1.1 me{~ OH/g) N 2.03/1.79 ~:.
Bll 1.0 g 4.8 g C -/36.18 :
(2.25 mmol) (86.5%) H-/8.08 Gluconarnidopropyl- N-/1.03 methyldimethylsiloxane copolymer 4.55g (6.495 meq OH/g) ProductB9= Z--O--(CH2)3-SI~O-S~ 4o(CH2)3 0--Z

~roduct B10 = Z--O--(CH2)3- Si--(O-Si)--23(CH2)3- 0--Z

j :: - ~ ' : , ' . ' ~
~:''' ~ ~ : ' 2~ ~J~

Product B 11 = (CH3)3Si~ O ~ O ~ Si(CH3)3 L CHS ) a (Cl H2)3) b c NH
C = O a:b = 12:1 c=3 (CHOH)4 ExamPle B12: Cyclodextrin macroinitiator Cyclodextrins are cyclic oligosaccharides of the formula \
~0~~' OH n in which n is a number from 6 to 8. They are commercial and hydroxyalkylated derivadves having a degree of subsdtudon of from 0.6 to 1.6 per dextrin unit.

The reaction with the photoinida~ors according to the invention generally gives mixtures comprising derivadves having various subsdtudon patterns and various degrees of subsdtudon. The preferred point of subsdtution is the prima~y hydroxyl group. ~emixtures can be separated by chromatography, where C6 monosubstituted derivatives with 6 to 8 photoinidators can readily be separated off. S g (4.4053 mmol) of dry ~cyclodextnn and 0.094 g of dibutyltin laurate are dissolved under dry nitrogen in 50 ml of dry dimethyl sulfoxide in a 250 ml flask made of brown glass fitted with reflux condenser, stilTer, internal thermometer and dropping funnel. A solution of 13.77 g (3.084 mmol) of the compound of Example Al in 50 ml of dry dime~yl sulfoxide is added dropwise to this solution at room temperature. The mixture is stirred first at room .

.

- 2~ ~7i~

temperature for 3 hours and subsequently at 50C for 15.5 hours, after which unreacted ,B-cyclodextrin can no longer be detected by chromatography. The reaction mixture is cooled, and the product is precipitated by addition of 1000 ml of dry diethyl ether. The isolated, viscous product is dissolved in 25 ml of acetone and re-precipitated by means of 500 ml of diethyl ether, giving a white suspension. The product is filtered off, and the white powder obtained is washed twice with 100 ml of diethyl ether and subsequently dried in vacuo with exclusion of light, giving 13.04 g t53.5 % of theory) of product. The ni~ogen content of 3.73 % corresponds to a mean degree of substitution of 5.6 per cyclodextrin ring. The product is fractionated by flash chromatography (column 60 cm in length,5 cm in diameter) on silica gel (Merck 60 F, grain size 0.04 to 0.063 mm) using methanoVtoluene (2:8) as eluent. With 13 g of crude product, the fol1Owing fracdons are obtained, fraction 2 being eluted with pure methanol and fraction 3 with methanol/water (1:1):

Fraction Amount( ) Ncontent(%) Meande reeofsubstitudon 1.3 4.25 6.4 2 3.59 3.59 5.4 3 1.36 1.36 2.0 C) Surface reacdon of polvmer films with the reactive Photoinitiator described in Example Al.

Examples Cl-C5: Fllms of various polymer materials containing reacdve groups arewetted on the surface with the soludon of the photoinitiator prepared as described in Example A 1 in a suitable so1vent (concentradon ~ 20 % by weight) by dipping, spraying or brushing. The films treated in this way are heated at 60C for 24 hours under dry nitrogen and subsequently freed from unreacted photoinitiator by washing with acetone.
After drying in the absence of light, the films are analysed by FTIR microscopy.

".
." ~ .
~ "

~-- 2 ~

Example Polymer film M n Solvent IR bands (cm-l) Cl Polyvinyl- ~70000 DMSO (ArC=C) 1600, 1510 alcohol (C~O) 1695 C2 Chitosan ~ 145 000 DMSO (Ar C=C) 1600, 1510 (C=O) 1690 C3 Collagen ~ 80 000 DMSO (Ar C=C) 1600, 1510 (C=O) 1695 C4 Polyvinyl- - MEK~l % DMSO (Ar C=C) 1600 alcohol con- (~O) 1705 taining 1 %
of TMDI

C5 Gluconamid~ ~ 4 000 MI~K+l % DMSO (Ar C= C) 1600, 1510 propylmethyl-dimethyl-siloxane copolymer, crosslinked with (C~) 1700 IPDI (20 % OH groups) ~K = methyl ethyl ketone Example C6: Surface reaction of a contact lens Con~ct lenses of crosslinked polyhydroxyethyl methacrylates (poly-HEMA) are wetted on the surface with a solution of compound Al in tetrahydro~uran (concentration 5 %) or diethyl ether. The treated contact lenses are stored at r~om temperature for 16 hours under dry nitrogen, then washed with acetone for 8 hours and then dried in a high vacuum.

D~ Surfaces - ~raft Polymerization with the modified polvmer films produced as in Examples Cl-C4 and N-vinYl-2-PYrrolidone - ~ .

.. . .
, . . .
.

.
,. :: ' , ~

2 11 ~

Examples Dl-D4: The polymer films of Examples Cl-C4 are wetted with freshly distilled N-vinyl-2-pyrrolidone by dipping, spraying or brushing, freed from oxygen by repeated evacuation and introduction of N2 gas and exposed to UV radiation from a mercuryhigh-pressure lamp in an N2 atmosphere (photoresist exposure machine 82420, Oriel). The films are subsequently washed several times with methanol in order to remove unpolymerized N-vinyl-2-pyrrolidone and unbonded homopolymer. The films are dried in vacuo and analysed by FTIR spectroscopy (IR bands of NVP).

Example UV irradiation FTIR bands (cm-l) duration Dl 20minutes 1510l (C=CAr); 1660(C=Ol NVP
1600J 1440-1470 ) D2 30minutes 1510l (C=CAr); 1660(C=0)NVP

D3 15 minutes 1600 (C=C Ar); 1660(C=O) NVP
D4 40 minutes 1600 (C=C Ar); 1675 (C=o7 NVP

Ar = aromatic, NVP = N-vinylpyrrolidone Exarnple D6: Modification of the surface of a contact lens.
Contact lenses treated as described in Example C6 are irnmersed in an aqueous solution of acrylamide and then freed from oxygen by repeated evacuation and interaction of nitrogen. The lenses are then irradiated twice for 2 minutes under nitrogen by means of a mercury high-pressure lamp (photoresist exposure machine 82420, Oniel, 2000 W). The contact lenses are then washed with distilled water and dried in a high vacuum. The contact lenses have the following values for the contact angle and contact angle hysteresis before (poly-HEMA) and after the treatment. The data show the good reproducibility.

~, , ,, ~ :, ~: ' ,, :
/

: 2 11 ~ 7 ~ J3 S~

Product Advancing Receding Hysteresis angle angle Poly-HEMA 78 33 44 Lens 1 from Example D6 54 49 5 Lens 2 from Example D6 49 41 8 Lens 3 from Example D6 53 48 5 9~
.'' :' ' ' : ' '"'`i"".' ' ' ~

, , .,: ~

Claims

1. A compound of the formula I or Ia (I), (Ia), in which X is O; Y is O, NH or NR6; Y1 is O; Y2 is -O-, -O-(O)C-, -C(O)-O- or -O-C(O)-O-; the n indices, independently of one another, are 0 or 1; R is H, C1-C12alkyl, C1-C12alkoxy or C1-C12alkyl-NH-; the R1 and R2 radicals, independently of one another, are H, linear or branched C1-C8alkyl, C1-C8hydroxyalkyl or C6-C10aryl, or two groups R1-(Y1)n- together are -(CH2)x-, or the R1-(Y1)n- and R2-(Y1)n- groups together form a radical of the formula ;

R3 is a direct bond or linear or branched C1-C8alkylene, which is unsubstituted or substituted by -OH and/or is uninterrupted or interrupted by one or more -O-, -O-C(O)- or -O-C(O)-O- groups; R4 is branched C3-C18alkylene, C6-C10arylene which is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy, C7-C18aralkylene which is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy, C3-C8cycloalkylene which is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy, C3-C8cycloalkylene-CyH2y- which is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy, or -CyH2y-(C3-C8cycloalkylene)-CyH2y- which is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy; each R5 independently has the same meaning as R4 or is linear C3-C18alkylene; R6 is linear or branched C1-C6alkyl; x is an integer from 3 to 5; y is an integer from 1 to 6, Ra and Rb, independently of one another, are H, C1-C8alkyl, C3-C8cycloalkyl, benzyl or phenyl; with the provisos that n in the -(Y1)n-R1 groups is 0 if R2 is H; that at most two Y1 radicals in the -(Y1)n- groups in the formula I are O and n in the other -(Y1)n- groups is 0; that at most one Y1 in the -(Y1)n- groups in the formula Ia is O and n in the other -(Y1)n- group is 0; and that n in the -(Y2)n- group is 0 if R3 is a direct bond.

2. A compound according to claim 1, wherein Y is O.

3. A compound according to claim 1, wherein Y2 is O.

4. A compound according to claim 1, wherein R is C1-C6alkyl or C1-C6alkoxy.

5. A compound according to claim 1, wherein R is C1-C4alkyl or C1-C4alkoxy.

6. A compound according to claim 1, wherein R is H.

7. A compound according to claim 1, wherein the alkyl and alkoxy substituents are methyl, ethyl, methoxy or ethoxy.

8. A compound according to claim 1, wherein alkyl R1 is linear C1-C4alkyl.

9. A compound according to claim 8, wherein R1 is methyl or ethyl.

10. A compound according to claim 1, wherein aryl R1 is phenyl.

11. A compound according to claim 1, wherein both R1-(Y1)n- groups are -(CH2)X-, in which x is 4 or 5.

12. A compound according to claim 1, wherein R2 is H, methyl or ethyl.

13. A compound according to claim 1, wherein R1 is ethyl or methyl or the two R1-(Y1)n-groups together are pentamethylene, n in the -(Y1)n-R2 group is O, R2 is methyl or H, and R is H.

14. A compound according to claim 1, wherein, in the -(Y1)n-R2 group, Y1 is O, n is 1 and R2 is H.

15. A compound according to claim 1, wherein, in the -(Y1)n-R2 group, Y1 is O, n is 1 and R2 is H, and n in the R1-(Y1)n- groups is 0.

16. A compound according to claim 1, wherein alkylene R3 contains 1 to 4 carbon atoms.

17. A compound according to claim 1, wherein R3 is ethylene, or R3 is a direct bond and n in the -(Y2)n- group is 0.

18. A compound according to claim 1, wherein R4 is branched C4-C10alkylene.

19. A compound according to claim 18, wherein R4 is 2,2-dimethyl-1,4-butylene, 2,2-di-methyl-1,5-pentylene, 2,2,3- or 2,2,4-trimethyl-1,5-pentylene, 2,2-dimethyl-1,6-hexylene, 2,2,3- or 2,2,4- or 2,2,5-trimethyl-1,6-hexylene, 2,2-dimethyl-1,7-heptylene, 2,2,3- or 2,2,4- or 2,2,5- or 2,2,6-trimethyl-1,7-heptylene, 2,2-dimethyl-1,8-octylene, 2,2,3- or 2,2,4- or 2,2,5- or 2,2,6- or 2,2,7-trimethyl-1,8-octylene.

20. A compound according to claim 1, wherein arylene R4 is phenylene, in particular phenylene which is substituted in the ortho-position to the XCN group.

21. A compound according to claim 20, wherein arylene R4 is 1-methyl-2,4-phenylene, 1,5-dimethyl-2,4-phenylene, 1-methoxy-2,4-phenylene or 1-methyl-2,7-naphthylene.

22. A compound according to claim 1, wherein aralkylene R4 is phenylalkylene having 1 to 6 carbon atoms in the alkylene group.

23. A compound according to claim 1, wherein cycloalkylene R4 is unsubstituted or methyl-substituted C5- or C6cycloalkyl.

24. A compound according to claim 23, wherein R4 is 1,3-cyclopentylene, 1,3- or 1,4-cyclohexylene, 4-methyl-1,3-cyclopentylene, 4-methyl-1,3-cyclohexylene, 4,4-dimethyl-1,3-cyclohexylene, 3-methyl- or 3,3-dimethyl-1,4-cyclohexylene, 3,5-dimethyl-1,3-cyclohexylene or 2,4-dimethyl-1,4-cyclohexylene.

25. A compound according to claim 1, wherein cycloalkylene-CyH2y-R4 is cyclohexylene-CyH2y- which is unsubstituted or substituted by 1 to 3 C1-C4alkyl groups.

26. A compound according to claim 25, wherein the -CyH2y- group is methylene.

27. A compound according to claim 23, wherein R4 is cyclopent-1-yl-3-methylene, 3-methylcyclopent-1-yl-3-methylene,3,4-dimethylcyclopent-1-yl-3-methylene, 3,4,4-trimethylcyclopent-1-yl-3-methylene, cyclohex-1-yl-3- or -4-methylene, 3- or 4- or 5-methylcyclohex-1-yl-3- or -4-methylene, 3,4- or 3,5-dimethylcyclohex-1-yl-3- or -4-methylene, 3,4,5- or 3,4,4- or 3,5,5-trimethylcyclohex-1-yl-3- or -4-methylene.

28. A compound according to claim 1, wherein -CyH2y-cycloalkylene-CyH2y- R4 is -CyH2y-cyclohexylene-CyH2y- which is unsubstituted or substituted by 1 to 3 C1-C4alkyl groups.

29. A compound according to claim 28, wherein the -CyH2y- group is methylene.

30. A compound according to claim 28, wherein R4 is cyclohexane-1,3- or -1,4-dimethylene, 3- or 4 or 5-methylcyclohexane-1,3- or -1,4-dimethylene, 3,4- or 3,5-dimethylcyclohexane-1,3- or -1,4-dimethylene or 3,4,5- or 3,4,4- or 3,5,5-trimethylcyclohexane-1,3- or 1,4-dimethylene.

31. A compound according to claim 1, wherein linear alkylene R5 contains 3 to 12 carbon atoms.

32. A compound according to claim 1, wherein R4 and Rs are alkylene which is branched in the .alpha.- or in particular .beta.-position to the XCN group, or are cyclic hydrocarbons substituted in at least one .alpha.-position as defined.

33. A compound according to claim 1, wherein the compound of the formula I or Ia is one in which n in the R1-(Y1)n- groups is 0, X, Y, Y2 and Y1 in the R2-(Y1)n- group are each O, n in the R2-(Y1)n- group is 0 or 1, R1 is C1-C4alkyl or phenyl, or the R1-(Y1)n- groups together are tetramethylene or pentamethylene, R2 is C1-C4alkyl or H, R is hydrogen, n in the -(Y2)n- group is 0 or 1, R3 is linear or branched C2-C4alkylene or a direct bond, in which case n in the -(Y2)n- group is 0, R4 is branched C5-C10alkylene, phenylene or phenylene which is substituted by 1 to 3 methyl groups, benzylene or benzylene which is substituted by 1 to 3 methyl groups, cyclohexylene or cyclohexylene which is substituted by 1 to 3 methyl groups, cyclohexyl-CyH2y- or -CyH2y-cyclohexyl-CyH2y- or cyclohexyl-CyH2y- or -CyH2y-cyclohexyl-CyH2y-, each of which is substituted by 1 to 3 methyl groups, R5 is as defined for R4 or is linear C3-C10alkylene, and y is 1 or 2.

34. A compound according to claim 1, wherein the compound of the formula I or Ia is one in which n in the R1-(Y1)-n and -(Y2)n- groups is 0, X, Y, Y2 and Y1 in the R2-(Y1)n- group are each O, n in the R2-(Y1)n- group is 0 or 1, R1 is methyl or phenyl or the R1-(Y1)n-groups together are pentamethylene, R2 is methyl or H, R is hydrogen, n in the -(Y2)-n group is 1 and R3 is ethylene, or n in the -(Y2)n- group is 0 and R3 is a direct bond, R4 is branched C6-C10alkylene, phenylene or phenylene which is substituted by 1 to 3 methyl groups, benzylene or benzylene which is substituted by 1 to 3 methyl groups, cyclohexylene or cyclohexylene which is substituted by 1 to 3 methyl groups, cyclohexyl-CH2- or cyclohexyl-CH2- which is substituted by 1 to 3 methyl groups, and R5 is as defined for R4 or is linear C5-C10alkylene.

35. A compound according to claim 1 having the formula .

36. A process for the preparation of a compound of the formula I or Ia, which comprises reacting a compound of the formula II or IIa (II), (IIa), in which Y, Y1, Y2, R, R1, R2, R3 and n are as defined in claim 1, with a diisocyanate of the formula III or IIIa XCN-R4-NCX (III), XCN-R5-NCX (IIIa), in which R4, R5 and X are as defined in claim 1, or a monoblocked diisocyanate of this type, in an inert organic solvent.

37. An oligomer or polymer containing H-active groups -OH and/or -NH- bonded to the oligomer or polymer backbone, if desired via a bridge group, or containing H-active -NH-groups bonded in the oligomer or polymer backbone, some or all of whose H atoms have been substituted by radicals of the formulae IV and/or IVa (IV), (IVa), in which R, R1, R2, R3, R4, R5, X, Y, Y1, Y2 and n are as defined in claim 1, bonded to the oligomer or polymer backbone.

38. An oligomer or polymer according to claim 37, wherein the oligomer has a mean molecular weight of from 300 to 10 000 daltons and the polymer has a mean molecular weight of from more than 10 000 to 1000 000.

39. An oligomer or polymer according to claim 37, wherein the oligomer or polymer containing H-active groups is a natural or synthetic oligomer.

40. An oligomer or polymer according to claim 39, which is a cyclodextrin, starch, hyaluronic acid, deacetylated hyaluronic acid, chitosan, trehalose, cellobiose, maltotriose, maltohexaose, chitohexaose, agarose, chitin 50, amylose, glucan, heparin, xylan, pectin, galactan, glycosaminoglycan, dextran, aminated dextran, cellulose, hydroxyalkylcellulose, carboxyalkylcellulose, heparin, fucoidan, chondroin sulfate, a sulfated polysaccharide, a mucopolysaccharide, gelatin, collagen, albumin, globulin, bilirubin, ovalbumin, keratin, fibronectin or vitronectin, pepsin, trypsin or lysozyme.

41. An oligomer or polymer according to claim 39, wherein a synthetic oligomer or polymer is a hydrolysed polymer of a vinyl ester or ether (polyvinyl alcohol), ahydroxylated polydiolefin, for example polybutadiene, polyisoprene or chloroprene;
polyacrylic acid, polymethacrylic acid or a polyacrylate, polymethacrylate, a polyacrylamide or a polymethacrylamide containing hydroxyalkyl or aminoalkyl radicals in the ester group or amide group; a polysiloxane containing hydroxyalkyl or aminoalkyl groups; a polyether made from epoxides or glycidyl compounds and a diol; a polyvinylphenol or a copolymer of vinylphenol and an olefinic comonomer; or a copolymer of at least one monomer from the group consisting of vinyl alcohol, hydroxyalkyl- or aminoalkyl-containing acrylates and methacrylates, acrylamide, methacrylamide, acrylic acid, methacrylic acid, and hydroxylated diolefins with an ethylenically unsaturated comonomer, for example vinylpyrrolidone, acrylonitrile, an olefin, a diolefin, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene, .alpha.-methylstyrene, a vinyl ether or a vinyl ester; or a polyoxaalkylene containing terminal OH or aminoalkoxy groups.

42. An oligomer or polymer according to claim 39, which is a cyclodextrin containing a total of 6 to 8 ring-forming glucose structural units or a hydroxyalkyl or aminoalkyl derivative or a glucose- or maltose-substituted derivative in which at least one structural unit conforms to the formula XVI

(XVI), in which R8, R9 and R10, independently of one another, are H, C1-C4alkyl, C2-C6acyl, C1-C4hydroxyalkyl or C2-C10aminoalkyl, and at least one of the radicals R8, R9 and R10 is a radical of the formulae V and/or Va (V), IMG> (Va), in which R, R1, R2, R3, R4, R5, X, Y, Y1, Y2 and n are as defined in claim 1, and R11 is a direct bond, -(C1-C4alkylene-O)- or -(C2-C10alkylene-NH)-.

43. An oligomer or polymer according to claim 41, which is an oligo- or polysiloxane containing, in terminal groups or side chains, OH or NH2 groups whose H atoms have been substituted by a photoinitiator according to claim 1.

44. An oligomer or polymer according to claim 43, which is an oligomer or polymer comprising a) from 5 to 100 mol % of structural units of the formula VI

(VI), and b) from 95 to 0 mol % of structural units of the formula VIa (VIa) based on the oligomer or polymer, where R12 is unsubstituted or F-substituted C1-C4alkyl, vinyl, allyl or phenyl, preferably methyl, R13 is C2-C6alkylene, preferably 1,3-propylene, R15 is as defined for R12 or is -R13-X1-H or -R13-X1-R16-H, X1 is -O- or -NH-, and R14 is a radical of the formulae VII or VIIa, (VII), (VIIa), in which R, R1, R2, R3, R4, R5, X, Y, Y1, Y2 and n are as defined in claim 1, and R16 is a direct bond or a -C(O)-(CHOH)r-CH2-O- group, in which r is 0 or an integer from 1 to 4.

45. An oligomer or polymer according to claim 43, which is an oligomeric or polymeric siloxane of the formula VIII

(VIII), where R12 is unsubstituted or F-substituted C1-C4alkyl, vinyl, allyl or phenyl, R13 is C2-C6alkylene, R15 is as defined for R12 or is -R13-X1-H or -R13-X1-R16-H, X1 is -O- or -NH-, and R14 is a radical of the formulae VII or VIIa, (VII), (VIIa), in which R, R1, R2, R3, R4, R5, X, Y, Y1, Y2 and n are as defined in claim 1, and R16 is a direct bond or a -C(O)-(CHOH)r-CH2-O- group, in which r is 0 or an integer from 1 to 4.

46. An oligomer or polymer according to claim 41, which is an oligomer or polymer comprising a) from 5 to 100 mol % of structural units of the formula IX

(IX), and b) from 95 to 0 mol % of structural units of the formula X

(X) in which R17 is a radical of the formula V or Va (V), (Va), in which R, R1, R2, R3, R4, R5, X, Y, Y1, Y2 and n are as defined in claim 1, and R11 is a direct bond, -(C1-C4alkylene-O)- or -(C2-C10alkylene-NH)-; R18 is H, C1-C6alkyl,-COOR21 or -COO?, R19 is H, F, Cl, CN or C1-C6alkyl, and R20 is H, OH, R11-H, F, Cl, CN, R21-O-, C1-C12alkyl, -COO?, -COOR10, -OCO-R10, methylphenyl or phenyl, whereR21 is C1-C18alkyl, C5-C7cycloalkyl, (C1-C12alkyl)-C5-C7cycloalkyl, phenyl, (C1-C12alkyl)phenyl, benzyl or (C1-C12alkyl)benzyl.

47. An oligomer or polymer according to claim 41, which is an oligomer or polymer comprising a) from 5 to 100 mol % of structural units of the formula XI

(XI), and b) from 95 to 0 mol % of structural units of the formula XII

(XII) in which R22 is H or methyl X2 and X3, independently of one another, are -O- or -NH-, R23 is -(CH2)c-, and c is an integer from 2 to 12, preferably from 2 to 6, R24 is a radical of the formula VII or VIIa, R18 and R19 are as defined in claim 46, and R25 is as defined for R20 or is -C(O)X2R23X3H.

48. An oligomer or polymer according to claim 41, which is a polyoxaalkylene oxide of the formula XIII containing identical or different recurring structural units , (XIII), in which R26 is a R29-X4- group or the v-valent radical of an alcohol or polyol having 1 to 20 carbon atoms, R27 is H, C1-C8alkyl, preferably C1-C4alkyl, particularly preferably methyl, R28 together with X4 is a direct bond or R28 is C2-C6alkylene, preferably C3-C6alkylene, particularly preferably 1,3-propylene, X4 is -O- or -NH-, R29 is a radical of the formula VII or VIIa, u has a numerical value of from 3 to 10 000, and v is an integer from 1 to 6.

49. A compound of the formula XIV or XIVa, (XIV), (XIVa), in which X, Y, Y1, Y2, R, R1, R2, R3, R4, R5 and n are as defined in claim 1, and R30 is a radical of the formula XV

(XV) in which R31 is H or methyl, R32 is branched or linear C2-C12alkylene, and X5 and X6, independently of one another, are -O- or -NH-.

50. A radiation-sensitive composition comprising a) at least one ethylenically unsaturated, photopolymerizable or photocrosslinkable compound and b) an amount, effective as initiator, of at least one compound of the formula I, Ia, XIV or XIVa or of an oligomer or polymer containing structural units of the formulae IV and IVa.

51. A radiation-sensitive composition according to claim 50, wherein the compounds of component b) are present in an amount of from 0.001 to 70 % by weight, based on component a).

52. A material comprising (a) an inorganic or organic substrate to whose surface is bonded (b) as photoinitiator, at least one compound of the formula I or Ia, as defined in claim 1, which is strongly bonded to the substrate via O atoms, S atoms, N-C1-C6alkyl groups or NH groups and the isocyanate group of the photoinitiators.

53. A material according to claim 52 comprising a transparent, organic base material which is an ophthalmic moulding, in particular a contact lens.

54. A material according to claim 52, wherein the photoinitiator coating is additionally coated by (c) a thin, external polymer coating obtainable by applying a thin coating of photopolymerizable, ethylenically unsaturated substances to the substrate surface provided with photoinitiator radicals, and polymerizing the coating of ethylenically unsaturated substances by irradiation, preferably with UV radiation.

55. A material according to claim 54, which is a contact lens.

56. A process for modifying surfaces of inorganic or organic substrates containing H-active HO-, HS-, -HN-C1-C6alkyl or -NH2 groups, comprising the steps a) application of a thin coating of photoinitiators of at least one compound of the formula I
or Ia to the substrate, b) binding the photoinitiators, if necessary with warming of the coated material, and washing off the excess photoinitiator, c) application of a thin coating of photopolymerizable, ethylenically unsaturated substances to the substrate surface provided with photoinitiator radicals, and d) polymerization of the coating of ethylenically unsaturated substances by irradiation, preferably with UV radiation.

57. A contact lens comprising (a) a transparent, organic base material containing functional groups, and (b) a thin surface coating comprising (b1) at least one photoinitiator of the formula I or Ia and (b2) a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

58. A contact lens comprising an oligomer or polymer according to claim 37 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

59. A contact lens comprising an oligomer or polymer according to claim 38 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

60. A contact lens comprising an oligomer or polymer according to claim 39 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

61. A contact lens comprising an oligomer or polymer according to claim 40 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

62. A contact lens comprising an oligomer or polymer according to claim 41 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

63. A contact lens comprising an oligomer or polymer according to claim 42 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

64. A contact lens comprising an oligomer or polymer according to claim 43 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

65. A contact lens comprising an oligomer or polymer according to claim 44 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

66. A contact lens comprising an oligomer or polymer according to claim 45 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

67. A contact lens comprising an oligomer or polymer according to claim 46 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

68. A contact lens comprising an oligomer or polymer according to claim 47 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

69. A contact lens comprising an oligomer or polymer according to claim 48 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

70. A contact lens comprising an oligomer or polymer of a compound according to claim 49 and a thin outer coating, on at least part of the surface, of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

71. A polymer obtainable by photopolymerization or photocrosslinking of a composition according to claim 50.

72. A polymer according to claim 71 to whose surface is applied a thin coating of a graft polymer formed by photopolymerization of a non-volatile or low-volatility olefin.

73. An ophthalmic moulding, in particular a contact lens, made from a polymer according to claim 72.