초록 ▼

Compounds of the formulae I, II, III and IV [ STR 1 ] wherein Ar for example is a phenyl, biphenyl or benzoylphenyl group, which is unsubstituted or substituted; Ar.sub.1, for example, has the same meanings as Ar; Ar.sub.2 is inter alia phenyl; X may be a direct bond; Y hydrogen, etc.; R.sub.1 and R

Compounds of the formulae I, II, III and IV [ STR 1 ] wherein Ar for example is a phenyl, biphenyl or benzoylphenyl group, which is unsubstituted or substituted; Ar.sub.1, for example, has the same meanings as Ar; Ar.sub.2 is inter alia phenyl; X may be a direct bond; Y hydrogen, etc.; R.sub.1 and R.sub.2 for example C.sub.1 -C.sub.8 alkyl; R.sub.3 inter alia hydrogen or C.sub.1 -C.sub.12 alkyl; R.sub.4 is inter alia C.sub.1 -C.sub.12 alkyl; or R.sub.3 and R.sub.4 together are C.sub.3 -C.sub.7 alkylene; R.sub.5 is for example C.sub.1 -C.sub.6 alkylene; and Z is a divalent radical; provided that at least one of the radicals Ar, Ar.sub.1, Ar.sub.2, Ar.sub.3, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 or Y is substituted by 1 to 5 SH groups, or provided that Y contains at least one --SS-- group, are photoinitiators for the polymerization of ethylenically unsaturated compounds.

대표청구항 ▼

[ What is claimed is:] [8.] A composition comprising(a) a polymer or oligomer having at least two ethylenically unsaturated groups and at least one carboxyl function within the molecule structure and(b) as photoinitiator, at least one compound of the formula I, II, III or IV [ STR 66 ] wherein a is

[ What is claimed is:] [8.] A composition comprising(a) a polymer or oligomer having at least two ethylenically unsaturated groups and at least one carboxyl function within the molecule structure and(b) as photoinitiator, at least one compound of the formula I, II, III or IV [ STR 66 ] wherein a is an integer 1, 2 or 4;Ar is a phenyl, biphenyl or benzoylphenyl group, which is unsubstituted or substituted by 1 to 5 of the radicals halogen, C.sub.1 -C.sub.12 alkyl, C.sub.3 -C.sub.12 alkenyl, C.sub.5 -C.sub.6 cycloalkyl, phenyl-C.sub.1 -C.sub.3 alkyl, --COOH, --COO(C.sub.1 -C.sub.4 alkyl), --OR.sub.7, --SH, --SR.sub.8, --SOR.sub.8, --SO.sub.2 R.sub.8, --CN, --SO.sub.2 NH.sub.2, --SO.sub.2 NH(C.sub.1 -C.sub.4 alkyl), --SO.sub.2 --N(C.sub.1 -C.sub.4 alkyl).sub.2, --NR.sub.9 R.sub.10, --NHCOR.sub.9, or by a group of the formula V, [ STR 67 ] or Ar is a group of the formula VI or VII [ STR 68 ] Ar.sub.1 if a is 1 has the same meanings as Ar; if a is 2, Ar.sub.1 is a divalent aromatic radical of the formula VIII or VIIIa [ STR 69 ] if a is 4, Ar.sub.1 is a tetravalent aromatic radical of the formula VIIIb [ STR 70 ] Ar.sub.2 is [ STR 71 ] these groups are unsubstituted or substituted by 1 to 5 of the radicals halogen, C.sub.1 -C.sub.12 alkyl, C.sub.3 -C.sub.12 alkenyl, C.sub.5 -C.sub.6 cycloalkyl, phenyl-C.sub.1 -C.sub.3 alkyl, --COOH, --COO(C.sub.1 -C.sub.4 alkyl), --OR.sub.7, --SH, --SR.sub.8, --SOR.sub.8, --SO.sub.2 R.sub.8, --CN, --SO.sub.2 NH.sub.2, --SO.sub.2 NH(C.sub.1 -C.sub.4 alkyl), --SO.sub.2 --N(C.sub.1 -C.sub.4 alkyl).sub.2, --NR.sub.9 R.sub.10, --NHCOR.sub.9, or by a group of the formula V as defined above, or Ar.sub.2 is a group of the formula VIa or VIIa [ STR 72 ] X is a direct bond, --O--, --S-- or --N(R.sub.6)--; Y is hydrogen, C.sub.1 -C.sub.12 alkyl, which is unsubstituted or substituted by 1 to 5 OH, OR.sub.6, COOR.sub.6, SH, N(R.sub.6).sub.2 or halogen or substituted 1 to 5 times by a group of the formula Ia [ STR 73 ] or Y is C.sub.2 -C.sub.20 alkyl, which is interrupted by 1 to 9 --O--, --N(R.sub.6)--, --S--, --SS--, --X--C(.dbd.O)--, --X--C(.dbd.S)--, --C(.dbd.O)--X--, --X--C(.dbd.O)--X--, --C(.dbd.S)--X--, [ STR 74 ] wherein the interrupted C.sub.2 -C.sub.20 alkyl can further be substituted by 1 to 5 SH, or Y is benzyl which is unsubstituted or substituted once or twice by --CH.sub.2 SH and said benzyl may further be substituted by C.sub.1 -C.sub.4 alkyl, or Y is Ar (as defined above), or a group [ STR 75 ] or Y is a heterocyclic 5-7 membered aliphatic or aromatic ring, comprising 1 to 4 N, O or/and S-atoms, or Y is a 8-12 membered bicyclic aliphatic or aromatic ring system, comprising 1 to 6 N, O or/and S-atoms, which mono- or bicyclic rings can further be substituted by SH or 1-5 times by a group of the formula Ia, or Y is a group [ STR 76 ] q is 1 or 2; r is 1, 2 or 3;p is 0 or 1;t is 1 to 6;u is 2 or 3;R.sub.1 and R.sub.2 independently of one another are C.sub.1 -C.sub.8 alkyl, which is unsubstituted or substituted by OH, C.sub.1 -C.sub.4 alkoxy, SH, CN, --COO(C.sub.1 -C.sub.8 alkyl), (C.sub.1 -C.sub.4 alkyl)-COO-- or --N(R.sub.3)(R.sub.4), or R.sub.1 and R.sub.2 independently of one another are C.sub.3 -C.sub.6 alkenyl, phenyl, chlorophenyl, R.sub.7 --O-phenyl, R.sub.8 --S-phenyl or phenyl-C.sub.1 -C.sub.3 -alkyl, wherein said C.sub.3 -C.sub.6 alkenyl, phenyl, chlorophenyl, R.sub.7 --O-phenyl, R.sub.8 --S-phenyl or phenyl-C.sub.2 -C.sub.3 -alkyl are unsubstituted or substituted by 1 to 5 SH, or R.sub.1 and R.sub.2 together are unbranched or branched C.sub.2 -C.sub.9 alkylene, C.sub.3 -C.sub.9 oxaalkylene or C.sub.3 -C.sub.9 azaalkylene, wherein said C.sub.2 -C.sub.9 alkylene, C.sub.3 -C.sub.9 oxaalkylene or C.sub.3 -C.sub.9 azaalkylene are unsubstituted or substituted by 1 to 5 SH or R.sub.1 and R.sub.2 independently of one another area radical of the formula IX or X [ STR 77 ] R.sub.3 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.2 -C.sub.4 alkyl, which is substituted by OH, SH, C.sub.1 -C.sub.4 alkoxy, CN or --COO(C.sub.1 -C.sub.4 alkyl), or R.sub.3 is C.sub.3 -C.sub.5 alkenyl, C.sub.5 -C.sub.12 -cycloalkyl or phenyl-C.sub.1 -C.sub.3 alkyl;R.sub.4 is C.sub.1 -C.sub.12 alkyl, C.sub.2 -C.sub.4 alkyl, which is substituted by OH, SH, C.sub.1 -C.sub.4 alkoxy, CN or --COO(C.sub.1 -C.sub.4 alkyl), or R.sub.4 is C.sub.3 -C.sub.5 alkenyl, C.sub.5 -C.sub.12 -cycloalkyl, phenyl-C.sub.1 -C.sub.3 alkyl, unsubstituted phenyl or phenyl, which is substituted by halogen, C.sub.1 -C.sub.12 alkyl, C.sub.1 -C.sub.4 alkoxy or --COO(C.sub.1 -C.sub.4 alkyl);or R.sub.4 together with R.sub.2 is C.sub.1 -C.sub.7 alkylene, phenyl-C.sub.1 -C.sub.4 alkylene, o-xylylene, 2-butenylene or C.sub.2 -C.sub.3 oxaalkylene or C.sub.2 -C.sub.3 azaalkylene;or R.sub.3 and R.sub.4 together are C.sub.3 -C.sub.7 alkylene, which can be interrupted by --O--, --S--, --CO-- or --N(R.sub.6)-- and which C.sub.3 -C.sub.7 alkylene can be substituted by OH, C.sub.1 -C.sub.4 alkoxy or --COO(C.sub.1 -C.sub.4 alkyl);R.sub.5 is C.sub.1 -C.sub.6 alkylene, xylylene, cyclohexylene, wherein said C.sub.1 -C.sub.6 alkylene, xylylene, cyclohexylene are unsubstituted or substituted by 1 to 5 SH, or R.sub.5 is a direct bond;R.sub.6 is hydrogen, unsubstituted or OH--, SH-- or HS--(CH.sub.2).sub.q --COO-substituted C.sub.1 -C.sub.12 alkyl, C.sub.2 -C.sub.12 alkyl, which is interrupted by --O--, --NH-- or --S--, or R.sub.6 is C.sub.3 -C.sub.5 alkenyl, phenyl-C.sub.1 -C.sub.3 alkyl, CH.sub.2 CH.sub.2 CN, unsubstituted or OH- or SH-substituted C.sub.1 -C.sub.4 alkyl-CO--CH.sub.2 CH.sub.2 --, unsubstituted or OH- or SH-substituted C.sub.2 -C.sub.8 alkanoyl or R.sub.6 is benzoyl;Z is a divalent radical of the formula [ STR 78 ] --N(R.sub.17)-- or --N(R.sub.17)--R.sub.18 --N(R.sub.17)--; U is unbranched or branched C.sub.1 -C.sub.7 alkylene;V and W independently of one another are a direct bond, --O--, --S-- or --N(R.sub.6)--, provided that V and W are not both a direct bond simultaneously;M is O, S or N(R.sub.6);R.sub.7 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.3 -C.sub.12 -alkenyl, cyclohexyl, hydroxycyclohexyl, or R.sub.7 is C.sub.1 -C.sub.4 alkyl, which is mono- or polysubstituted with Cl, Br, CN, SH, --N(C.sub.1 -C.sub.4 alkyl).sub.2, piperidino, morpholino, OH, C.sub.1 -C.sub.4 alkoxy, --OCH.sub.2 CH.sub.2 CN, --OCH.sub.2 CH.sub.2 COO(C.sub.1 -C.sub.4 alkyl), --OOCR.sub.19, --COOH, --COO(C.sub.1 -C.sub.8 alkyl), --CONH(C.sub.1 -C.sub.4 alkyl), --CON(C.sub.1 -C.sub.4 alkyl).sub.2, [ STR 79 ] --CO(C.sub.1 -C.sub.4 alkyl) or [ STR 80 ] or R.sub.7 is 2,3-epoxypropyl, --(CH.sub.2 CH.sub.2 O).sub.m H, unsubstituted phenyl, or phenyl which is substituted by halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or --COO(C.sub.1 -C.sub.4 alkyl), or R.sub.7 is phenyl-C.sub.1 -C.sub.3 alkyl, tetrahydropyranyl, tetrahydrofuranyl, --COOR.sub.19, --COO(C.sub.1 -C.sub.8 alkyl), --CONH(C.sub.1 -C.sub.4 alkyl), --CON(C.sub.1 -C.sub.8 alkyl).sub.2, --Si(R.sub.20)(R.sub.21).sub.2, or --SO.sub.2 R.sub.22 ;R.sub.8 is C.sub.1 -C.sub.12 alkyl, C.sub.3 -C.sub.12 alkenyl, cyclohexyl, hydroxycyclohexyl, or R.sub.8 is C.sub.1 -C.sub.4 alkyl, which is mono- or polysubstituted with Cl, Br, CN, SH, --N(C.sub.1 -C.sub.4 alkyl).sub.2, piperidino, morpholino, OH, C.sub.1 -C.sub.4 alkoxy, --OCH.sub.2 CH.sub.2 CN, --OCH.sub.2 CH.sub.2 COO(C.sub.1 -C.sub.4 alkyl), --OOCR.sub.19, --COOH, --COO(C.sub.1 -C.sub.8 alkyl), --CON(C.sub.1 -C.sub.4 alkyl).sub.2, [ STR 81 ] --CO(C.sub.1 -C.sub.4 alkyl) or [ STR 82 ] or R.sub.8 is 2,3-epoxypropyl, phenyl-C.sub.1 -C.sub.3 alkyl, phenyl-C.sub.1 -C.sub.3 hydroxyalkyl, unsubstituted phenyl or phenyl which is mono- or poly-substituted by halogen, SH, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or --COO(C.sub.1 -C.sub.4 alkyl), or R.sub.8 is 2-benzothiazyl, 2-benzimidazolyl, --CH.sub.2 CH.sub.2 --O--CH.sub.2 CH.sub.2 --SH or --CH.sub.2 CH.sub.2 --S--CH.sub.2 CH.sub.2 --SH;R.sub.9 and R.sub.10 independently of one another are hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.2 -C.sub.4 alkyl, which is substituted by OH, SH, C.sub.1 -C.sub.4 alkoxy, CN or --COO(C.sub.1 -C.sub.4 alkyl), or R.sub.9 and R.sub.10 independently of one another are C.sub.3 -C.sub.5 alkenyl, cyclohexyl, phenyl-C.sub.1 -C.sub.3 alkyl, unsubstituted phenyl or phenyl which is mono- or poly-substituted by C.sub.1 -C.sub.12 alkyl or halogen, or R.sub.9 and R.sub.10 together are C.sub.2 -C.sub.7 alkylene which can be interrupted by --O--, --S-- or --N(R.sub.18)--;R.sub.11 and R.sub.12 independently of one another are a direct bond, --CH.sub.2 --, --CH.sub.2 CH.sub.2 --, --O--, --S--, --CO-- or --N(R.sub.6)--; provided that R.sub.11 and R.sub.12 are not a direct bond at the same time;R.sub.13 is hydrogen, C.sub.1 -C.sub.8 alkyl or phenyl wherein C.sub.1 -C.sub.8 alkyl or phenyl are unsubstituted or substituted by 1 to 5 SH;R.sub.14, R.sub.15 and R.sub.16 independently of one another are hydrogen or unsubstituted or SH-substituted C.sub.1 -C.sub.4 alkyl;R.sub.17 is hydrogen, unsubstituted or SH-substituted C.sub.1 -C.sub.8 alkyl or unsubstituted or SH-substituted phenyl;R.sub.18 is unbranched or branched C.sub.2 -C.sub.16 alkylene, which can be interrupted by 1 to 6 --O--, --S-- or --N(R.sub.17)-- or substituted by 1 to 5 groups SH;R.sub.19 is C.sub.1 -C.sub.4 alkyl, C.sub.2 -C.sub.4 alkenyl or phenyl;R.sub.20 and R.sub.21 independently of one another are C.sub.1 -C.sub.4 alkyl or phenyl;R.sub.22 is C.sub.1 -C.sub.18 alkyl, phenyl or phenyl substituted by C.sub.1 -C.sub.14 alkyl;Ar.sub.3 is phenyl, naphthyl, furyl, thienyl or pyridiyl, wherein said radicals are unsubstituted or substituted by halogen, SH, OH, C.sub.1 -C.sub.12 alkyl, C.sub.1 -C.sub.4 alkyl, which is substituted by OH, halogen, SH, --N(R.sub.17).sub.2, C.sub.1 -C.sub.12 alkoxy, --COO(C.sub.1 -C.sub.18 alkyl), --CO(OCH.sub.2 CH.sub.2).sub.n OCH.sub.3 or --OCO(C.sub.1 -C.sub.4 alkyl), or said radicals are substituted by C.sub.1 -C.sub.12 alkoxy, C.sub.1 -C.sub.4 alkoxy, which is substituted by --COO(C.sub.1 -C.sub.18 alkyl) or --CO(OCH.sub.2 CH.sub.2).sub.n OCH.sub.3, or said radicals are substituted by --(OCH.sub.2 CH.sub.2).sub.n OH, --(OCH.sub.2 CH.sub.2).sub.n OCH.sub.3, C.sub.1 -C.sub.8 alkylthio, phenoxy, --COO(C.sub.1 -C.sub.18 alkyl), --CO(OCH.sub.2 CH.sub.2).sub.n OCH.sub.3, phenyl or benzoyl;n is 1 to 20;m is 2 to 20; vided that at least one of the radicals Ar, Ar.sub.1, Ar.sub.2, Ar.sub.3, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 or Y is substituted by 1 to 5 SH groups, or provided that Y contains at least one --SS-- group; or an acid addition salt of a compound of the formula I, II, III or IV.