Oxime ester photoinitiators

A compound of formula I

• wherein
• R1 is hydrogen, (CO)R″2, C1-C20alkoxycarbonyl, phenyl-C1-C4alkyl, C1-C20alkyl which optionally is substituted by one or more halogen, COOR11, CONR12R13;
• or
• R1 is C2-C20alkyl which is interrupted by O, CO or NR14;
• C2-C12alkenyl which optionally is interrupted by O, CO or NR14, or is C4-C8cycloalkenyl or C2-C12alkinyl;
• or
• R1 is benzoyl, naphthoyl, phenyloxycarbonyl or naphtyloxycarbonyl;
• or is benzoyl, naphthoyl, phenyloxycarbonyl or naphtyloxycarbonyl each of which is optionally substituted by one or more C1-C20alkyl, C1-C4haloalkyl, SR10, OR11, NR12R13, halogen, phenyl, COOR11, CONR12R13, CN, NO2 or C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or
• R1 is C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14, C3-C10cycloalkylcarbonyl which optionally is interrupted by O, CO or NR14, C3-C10cycloalkyloxycarbonyl which optionally is interrupted by O, CO or NR14;
• or R1 is unsubstituted phenyl or naphthyl, or is phenyl or naphthyl which is substituted by one or more C1-C20alkyl, C1-C4haloalkyl, SR10, OR11, NR12R13, halogen, phenyl, COOR11, CONR12R13, CN, NO2, or C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• R2 and R′2 independently of each other are hydrogen, C1-C20alkyl, C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14
• or R2- and R′2 are C1-C20alkyl optionally substituted by one or more halogen, OR11, COOR11, CONR12R13, phenyl or phenyl substituted by SR10, OR11, or NR12R13;
• or
• R2 and R′2 are C2-C20alkyl interrupted by one or more O and/or optionally substituted by one or more halogen, OR11, COOR11, CONR12R13, phenyl or phenyl substituted by SR10, OR11, or NR12R13;
• or
• R2 and R′2 are unsubstituted phenyl or naphthyl or are phenyl or naphthyl which is substituted by one or more C1-C12alkyl, phenyl, halogen, CN, NO2, SR10, OR11, NR12R13 or by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or
• R2 and R′2 are C2-C20alkanoyl, or benzoyl which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, SR10, OR11, NR12R13;
• or
• R2 and R′2 are C2-C12alkoxycarbonyl optionally interrupted by one or more O and/or optionally substituted by one or more OH;
• or
• R2 and R′2 are phenoxycarbonyl which is unsubstituted or substituted by one or more C1-C6alkyl, halogen, phenyl, SR10, OR11 or NR12R13;
• R″2 has one of the meanings given for R2 and R′2 or is
• R3, R4, and R5 independently of one another are hydrogen, C1-C20alkyl, C2-C20alkyl which is interrupted by O, CO or NR14, C2-C12alkenyl which optionally is interrupted by O, CO or NR14, or are C4-C8cycloalkenyl, C2-C12alkinyl, phenyl-C1-C4alkyl, CN, NO2 or C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or R3, R4, and R5 are phenyl which is unsubstituted or substituted by one or more SR10, OR11 or NR12R13;
• or R3, R4, and R5 are (CO)R′2, SR10, OR11, SOR10, SO2R10 or NR12R13, wherein the substituents (CO)R′2, OR11, SR10 and NR12R13 optionally form 5- or 6-membered rings via the radicals R10, R11, R12R13, and/or R′2 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring;
• provided that
• (i) at least one of R3, R4 or R5 is other than hydrogen or C1-C20alkyl;
• and that
• (ii) if one of R3, R4 or R5 is SR10 then R10 is not phenyl;
• and
• (iii) if one of R3, R4 or R5 is NR12R13, then R12 and R13 are not both C1-C20alkyl;
• and
• (iv) if one of R3, R4 or R5 is NR12R13 and R12 and R13 together with the N-atom to which they are attached form a ring, said ring is not a morpholino ring;
• and
• (v) if R3 is hydrogen, R4 is hydrogen or C1-C20alkyl in the ortho-position of the phenyl ring and R5 is OR11 in the para-position of the phenyl ring, then R11 is not C3-C10cycloalkyl or C3-C10cycloalkyl which is interrupted by O;
• R6, R7, R′6, and R′7, independently of one another have one of the meanings as given for R3, R4 and R5;
• R9 is hydrogen, C3-C8cycloalkyl, C2-C8alkenyl, C1-C20alkoxy, C1-C20alkyl which is substituted by one or more halogen, C1-C20alkylphenyl and/or CN;
• or R9 is naphthyl which is unsubstituted or substituted by one or more C1-C6alkyl, halogen, CN, OR11, SR10 and/or NR12R13;
• or R9 is benzyloxy or phenoxy both of which are unsubstituted or substituted by one or more C1-C6alkyl and/or halogen;
• R10 is hydrogen, C1-C20alkyl, C3-C12alkenyl, C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14, or R10 is phenyl-C1-C4alkyl;
• C1-C8alkyl which is substituted by OH, SH, CN, C3-C6alkenoxy, —OCH2CH2CN, —OCH2CH2(CO)O(C1-C4alkyl), —O(CO)—(C1-C4alkyl), —O(CO)-phenyl, —(CO)OH or —(CO)O(C1-C4alkyl);
• or R10 is C2-C20alkyl which is interrupted by one or more O or S;
• or R10 is —(CH2CH2O)nH, —(CH2CH2O)n(CO)—(C1-C8alkyl), C2-C8alkanoyl, benzoyl, C3-C12alkenyl, C3-C6alkenoyl;
• or R10 is phenyl or naphthyl, each of which is unsubstituted or substituted by one or more halogen, C1-C12alkyl, C1-C12alkoxy, phenyl-C1-C3alkyloxy, phenoxy, C1-C12alkylsulfanyl, phenylsulfanyl, —N(C1-C12alkyl)2, diphenylamino, —(CO)O(C1-C8alkyl) or (CO)N(C1-C8alkyl)2;
• or R10 is phenyl or naphthyl which forms a 5- or 6-membered ring with the phenyl ring to which the SR10 is attached via a direct bond, C1-C4alkylene, O, S, NR14 or CO, wherein said phenyl or naphthyl is unsubstituted or substituted by one or more C1-C20alkyl, C2-C20alkyl which is interrupted by O, CO or NR14, or is substituted by C3-C10cycloalkyl which is optionally interrupted by O, CO or NR14, or is substituted by halogen, C1-C20alkoxy, C1-C20alkylcarbonyl or phenylcarbonyl;
• n is an integer from 1-12;
• R11 is hydrogen, C1-C20alkyl which optionally is substituted by one or more halogen;
• or is —(CH2CH2O)nH, —(CH2CH2O)n(CO)—(C1-C8alkyl), C1-C8alkanoyl, C3-C12alkenyl, C3-C6alkenoyl, phenyl-C1-C4alkyl;
• C2-C20alkyl which is interrupted by one or more O;
• C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or R11 is C1-C8alkyl which is substituted by OH, SH, CN, C3-C6alkenoxy, —OCH2CH2CN, —OCH2CH2(CO)O(C1-C4alkyl), —O(CO)—(C1-C4alkyl), —O(CO)-phenyl, —(CO)OH or —(CO)O(C1-C4alkyl);
• or R11 is benzoyl which is unsubstituted or substituted by one or more C1-C6alkyl, halogen, OH or C1-C4alkoxy;
• or R11 is phenyl or naphthyl each of which is unsubstituted or substituted by one or more halogen, OH, C1-C12alkyl, C3-C10cycloalkyl or C1-C12alkoxy;
• R12 and R13 independently of one another are hydrogen, C1-C20alkyl, C2-C20alkyl which is interrupted by O, CO or NR14, C2-C4hydroxyalkyl, C1-C12alkoxy, phenyl-C1-C4alkyl, (CO)R15, C2-C10alkoxyalkyl, C3-C5alkenyl, C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or R12 and R13 are phenyl or naphthyl, each of which is unsubstituted or substituted by one or more C1-C20alkoxy, (CO)R15, phenyl, NR16R17, SR10, OR11, C1-C20alkyl, C2-C20alkyl which is interrupted by O, CO or NR14 or by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or R12 and R13 independently of each other are C2-C5alkylene or C2-C5alkenylene which is attached to one of the C-atoms of the phenyl or naphthyl ring to which the NR12R13 is attached, wherein said C2-C5alkylene or C2-C5alkenylene optionally is interrupted by O, CO or NR14;
• or
• R12 and R13 independently of one another are phenyl which is attached via a direct bond to the phenyl ring on which the NR12R13 is positioned;
• or
• R12 and R13 together with the N-atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which optionally is interrupted by O, N or NR14, and which ring is unsubstituted or substituted by one or more C1-C20alkyl, C1-C20alkoxy, ═O, SR10, OR11 or NR16R17, (CO)R15, NO2, CN, phenyl or by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or
• R12 and R13 together with the N-atom to which they are attached form a heteroaromatic ring system, which heteroaromatic ring system is unsubstituted or substituted by one or more C1-C20alkyl, C1-C20alkoxy, ═O, SR10, OR11, NR16R17, (CO)R15, NO2, CN, phenyl or by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• R14 is hydrogen, C1-C20alkyl, C3-C8cycloalkyl, phenyl or (CO)R15;
• R15 is OH, C1-C20alkyl, C2-C20alkyl which interrupted by O, CO or NR14, C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14, or is phenyl-C1-C4alkyl, SR10, OR11 or NR12R13;
• or R15 is phenyl or naphthyl both of which are unsubstituted or substituted by one or more SR10, OR11, NR12R13, CN, NO2, halogen, C1-C20alkyl, C2-C20alkyl which is interrupted by O, CO or NR14 or C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• R16 and R17 independently of each other are hydrogen, C1-C20alkyl, C3-C10cycloalkyl or phenyl;
• or
• R16 and R17 together with N-atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring, which optionally is interrupted by O, S or NR14;
• or R16 and R17 independently of one another are C2-C5alkylene or C2-C5alkenylene which is attached to one of the C-atoms of the phenyl or naphthyl ring to which the NR16R17 is attached, wherein said C2-C5alkylene or C2-C5alkenylene optionally is interrupted by O, CO or NR15, and to which C2-C5alkylene or C2-C5alkenylene optionally a benzene ring is condensed;
• R18, R19, R20, R′18, R′19, and R′20 independently of one another have one of the meanings as given for R6, R7, R′6, and R′7;
• and
• R″18 and R″19 together are C1-C6alkylene or C2-C6alkenylene to form a bicyclic ring together with the phenyl to which they are attached, wherein said bicyclic ring optionally is substituted by one or more C1-C20alkyl, C2-C20alkyl which is interrupted by O, CO or NR14, C1-C4haloalkyl, SR10, OR11, NR12R13, halogen, phenyl, COOR11, CONR12R13, CN, NO2, or C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• provided that the group
• is attached to either ring.