Oxime ester photoinitiators

Compounds of the formula I and I′

• wherein
• R1 and R′1 independently of one another are hydrogen, C3-C8cycloalkyl or C1-C12alkyl which is unsubstituted or substituted by one or more halogen, phenyl and/or CN;
• or
• R1 and R′1 are C2-C5alkenyl;
• or
• R1 and R′1 are phenyl which is unsubstituted or substituted by one or more C1-C6alkyl, halogen, CN, OR3, SR4 and/or NR5R6;
• or
• R1 and R′1 are C1-C8alkoxy, benzyloxy;
• or phenoxy which is unsubstituted or substituted by one or more C1-C6alkyl and/or halogen;
• R2 and R2′ independently of one another are hydrogen;
• unsubstituted C1-C20alkyl or C1-C20alkyl substituted by one or more halogen, OR3, SR4, C1-C20heteroaryl, C8-C20phenoxycarbonyl, C1-C20heteroaryloxycarbonyl, NR5R6, COOR3, CONR5R6,
• phenyl and/or by phenyl which is substituted by OR3, SR4 and/or NR5R6, wherein the unsubstituted or substituted C1-C20alkyl optionally contains one or more C—C multiple bonds;
• or
• R2 and R2′ are NR5R6,
• or C3-C20cycloalkyl;
• or are C2-C20alkyl which is interrupted by one or more O and which optionally is substituted by one or more halogen, OR3, phenyl and/or phenyl substituted by OR3, SR4 and/or NR5R6;
• or
• R2 and R2′ are phenyl which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, halogen, OR3, SR4 and/or NR5R6;
• or
• R2 and R2′ are C2-C20alkanoyl or benzoyl which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, OR3, SR4 and/or NR5R6;
• or
• R2 and R2′ are C2-C12alkoxycarbonyl which is optionally interrupted by one or more O and/or optionally substituted by one or more hydroxyl groups;
• or
• R2 and R2′ are phenoxycarbonyl which is unsubstituted or substituted by C1-C6alkyl, halogen, phenyl, OR3, SR4 and/or NR5R6;
• or
• R2 and R2′ are CN, CONR5R6, NO2, S(O)m—C1-C6alkyl;
• S(O)m-phenyl which optionally is substituted by C1-C12alkyl or SO2—C1-C6alkyl;
• or are SO2O-phenyl which optionally is substituted by C1-C12alkyl;
• or are diphenyl phosphinoyl or di-(C1-C4alkoxy)-phosphinoyl;
• or
• R2 and R2′ are
• m is 1 or 2;
• Ar3 is phenyl, naphthyl or coumarinyl, each of which is substituted once or more times by halogen, C1-C12alkyl, C3-C8cycloalkyl, benzyl and/or phenoxycarbonyl;
• or each of which is substituted by phenyl or by phenyl which is substituted by one or more OR3, SR4 and/or NR5R6;
• or each of which is substituted by C2-C12alkoxycarbonyl optionally interrupted by one or more O and/or optionally substituted by one or more hydroxyl groups;
• or each of which is substituted by OR3, SR4, SOR4, SO2R4 and/or NR5R6;
• M2 is a direct bond, cyclohexylene or C1-C10alkylene or C1-C10alkylene-X—, which C1-C10alkylene or C1-C10alkylene-X— is optionally interrupted by one or more O and/or optionally substituted by one or more halogen, OR3, phenyl or phenyl substituted by OR3, SR4 and/or NR5R6;
• or M2 is phenylene, naphthylene or phenylene-X—, each of which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, halogen, OR3, SR4 and/or NR5R6;
• or M2 is C1-C10alkylene-C(O)—X—, C1-C10alkylene-X—C(O)—, phenylene-C(O)—X— or C1-C10alkylene-phenylene-X—;
• M3 is a direct bond, cyclohexylene, C1-C10alkylene or C1-C10alkylene-X—, which C1-C10alkylene or C1-C10alkylene-X— is optionally interrupted by one or more O and/or optionally substituted by one or more halogen, OR3, phenyl or phenyl substituted by OR3, SR4 and/or NR5R6;
• or
• M3 is phenylene, naphthylene or phenylene-X—, each of which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, halogen, OR3, SR4 and/or NR5R6;
• or
• M3 is C1-C10alkylene-C(O)—X—, C1-C10alkylene-X—C(O)—, phenylene-C(O)—X—, C1-C10alkylene-phenylene-X— or phenylene-(CO)-phenylene;
• X is O, S or NR5;
• X1 is O, S, SO or SO2;
• X2 is a direct bond, C1-C20alkylene which optionally is interrupted by O, CO or NR5, and which uninterrupted or interrupted C1-C20alkylene is unsubstituted or substituted by one or more halogen, OR3, COOR3, NR5R6, C1-C20heteroaryl, C1-C20heteroaryl-(CO)O, C1-C20heteroaryl-S, CONR5R6,
• phenyl or by phenyl substituted by halogen, C1-C20alkyl, C1-C4haloalkyl, SR4, OR3, or NR5R6, and which unsubstituted or substituted, interrupted or non-interrupted C1-C20alkylene optionally contains one or more C—C multiple bonds;
• R3 is hydrogen, C1-C20alkyl or phenyl-C1-C3alkyl;
• or
• R3 is C1-C20alkyl which is substituted by OH, SH, —CN, C3-C6alkenoxy, OCH2CH2CN, OCH2CH2(CO)O(C1-C4alkyl), O(CO)—(C1-C4alkyl), O(CO)-phenyl, (CO)OH and/or (CO)O(C1-C4alkyl);
• or
• R3 is C2-C20alkyl which is interrupted by one or more O;
• or
• R3 is (CH2CH2O)n+1H, (CH2CH2O)n(CO)—(C1-C8alkyl), C1-C8alkanoyl, C2-C12alkenyl, C3-C6alkenoyl or C3-C20cycloalkyl which optionally is interrupted by O, S, CO, NR5;
• or
• R3 is benzoyl which is unsubstituted or substituted by one or more C1-C6alkyl, halogen, OH and/or C1-C4alkoxy;
• or
• R3 is phenyl, naphthyl or C1-C20heteroaryl, each of which is unsubstituted or substituted by halogen, OH, C1-C12alkyl, C1-C12alkoxy, CN, NO2, phenyl-C1-C3alkyloxy, phenoxy, C1-C12alkylsulfanyl, phenylsulfanyl, N(C1-C12alkyl)2, diphenylamino and/or
• n is 1-20;
• R4 is hydrogen, C1-C20alkyl, C2-C12alkenyl, C3-C20cycloalkyl, phenyl-C1-C3alkyl, wherein the C1-C20alkyl, C2-C12alkenyl, C3-C20cycloalkyl, phenyl-C1-C3alkyl optionally is interrupted by O, S, CO, NR5;
• or
• R4 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
• R4 is (CH2CH2O)n+1H, (CH2CH2O)n(CO)—(C1-C8alkyl), C1-C8alkanoyl, C2-C12alkenyl, C3-C6alkenoyl;
• or
• R4 is benzoyl which is unsubstituted or substituted by one or more C1-C6alkyl, halogen, —OH, C1-C4alkoxy or C1-C4alkylsulfanyl;
• or
• R4 is phenyl, naphthyl or C1-C20heteroaryl, each of which is unsubstituted or substituted by halogen, C1-C12alkyl, C1-C12alkoxy, CN, NO2, phenyl-C1-C3alkyloxy, phenoxy, C1-C12alkylsulfanyl, phenylsulfanyl, N(C1-C12alkyl)2, diphenylamino, (CO)O(C1-C8alkyl), (CO)—C1-C8alkyl, (CO)N(C1-C8alkyl)2 or
• R5 and R6 independently of each other are hydrogen, C1-C20alkyl, C2-C4hydroxyalkyl, C2-C10alkoxyalkyl, C2-C5alkenyl, C3-C20cycloalkyl, phenyl-C1-C3alkyl, C1-C8alkanoyl, C3-C12-alkenoyl, benzoyl;
• or
• R5 and R6 are phenyl, naphthyl or C1-C20heteroaryl, each of which is unsubstituted or substituted by C1-C12alkyl, benzoyl or C1-C12alkoxy;
• or
• R5 and R6 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, S or NR3, and which ring is unsubstituted or substituted by one or more C1-C20alkyl, C1-C20alkoxy, ═O, SR4, OR3 or NR17R18, (CO)R19, NO2, halogen, C1-C4haloalkyl, CN, phenyl,
• or by C3-C20cycloalkyl which optionally is interrupted by O, S, CO or NR3;
• or
• R5 and R6 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-C4haloalkyl, C1-C20alkoxy, ═O, SR4, OR3, NR17R18, (CO)R19,
• halogen, NO2, CN, phenyl or by C3-C20cycloalkyl which optionally is interrupted by O, S, CO or NR3;
• R″1 has one of the meanings as given for R1;
• R″2 has one of the meanings as given for R2;
• R7 is hydrogen, C1-C20alkyl;
• C1-C8alkyl which is substituted by halogen, phenyl, 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
• R7 is C2-C12alkyl which is interrupted by one or more O;
• or
• R7 is (CH2CH2O)n+1H, (CH2CH2O)n(CO)—(C1-C8alkyl), C2-C12alkenyl or C3-C8cycloalkyl;
• or
• R7 is phenyl, biphenylyl, naphthyl or C1-C20heteroaryl, each of which optionally is substituted by one or more C1-C20alkyl, halogen, C1-C12haloalkyl, CN, NO2, OR3, SR4, SOR4, SO2R4 or NR5R6, wherein the substituents OR3, SR4 or NR5R6 optionally form 5- or 6-membered rings via the radicals R3, R4, R5 and/or R6 with one of the carbon atoms of the phenyl, biphenylyl, naphthyl or C1-C20heteroaryl ring;
• R8 and R9 and R′8 and R′9 independently of each other are hydrogen, C1-C12alkyl which optionally is substituted by one or more halogen, phenyl, CN, OH, SH, C1-C4alkoxy, (CO)OH or (CO)O(C1-C4alkyl);
• or
• R8 and R9 and R′8 and R′9 are phenyl which optionally is substituted by one or more C1-C6alkyl, halogen, CN, OR3, SR4 or NR5R6;
• or
• R8 and R9 and R′8 and R′9 are halogen, CN, OR3, SR4, SOR4, SO2R4 or NR5R6, wherein the substituents OR3, SR4 or NR5R6 optionally form 5- or 6-membered rings via the radicals R3, R4, R5 and/or R6 with one of the carbon atoms of the phenyl or with the substituent R7 or one of the carbon atoms of the naphthylene or phenylene group of M3;
• or
• R8 and R9 and R′8 and R′9 together are
• R10, R11, R12 and R13 independently of one another are hydrogen, C1-C12alkyl which optionally is substituted by one or more halogen, phenyl, CN, OH, SH, C1-C4alkoxy, (CO)OH or (CO)O(C1-C4alkyl);
• or
• R10, R11, R12 and R13 are phenyl which optionally is substituted by one or more C1-C6alkyl, halogen, CN, OR3, SR4 or NR5R6;
• or
• R10, R11, R12 and R13 are halogen, CN, OR3, SR4 or NR5R6;
• R14 and R15 independently of each other are hydrogen, C1-C12alkyl which optionally is substituted by one or more halogen, phenyl, CN, OH, SH, C1-C4alkoxy, (CO)OH or (CO)O(C1-C4alkyl);
• or R14 and R15 are phenyl which optionally is substituted by one or more C1-C6alkyl, halogen, CN, OR3, SR4 or NR5R6;
• R17 and R18 independently of each other are hydrogen, C1-C20alkyl, C1-C4haloalkyl, C3-C10cycloalkyl or phenyl;
• or
• R17 and R18 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 NR24;
• or R17 and R18 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 NR17R18 is attached, wherein said C2-C5alkylene or C2-C5alkenylene optionally is interrupted by O, CO or NR24, and to which C2-C5alkylene or C2-C5alkenylene optionally a benzene ring is condensed;
• R19 is hydrogen, OH, C1-C20alkyl, C1-C4haloalkyl, C2-C20alkyl which is interrupted by O, CO or NR24, C3-C20cycloalkyl which optionally is interrupted by O, S, CO or NR24, or is phenyl, naphthyl, phenyl-C1-C4alkyl, SR4, OR3 or NR17R18;
• R20 is COOR3, CONR5R6, (CO)R1;
• or R20 has one of the meanings as given for R5 and R6;
• R21 is COOR3, CONR5R6, (CO)R1;
• or R21 has one of the meanings as given for R3;
• R22 is hydrogen, C1-C20alkyl;
• C2-C20alkenyl;
• C3-C20cycloalkyl which optionally is interrupted by O, S, CO or NR5, or is C3-C10cycloalkenyl;
• or is C1-C20alkyl which is substituted by one or more halogen, SR4, OR3, COOR3, NR5R6, C1-C20heteroaryl, C1-C20heteroaryl-(CO)O, CONR5R6,
• or phenyl;
• or R22 is C2-C20alkyl which is interrupted by one or more O and/or optionally is substituted by one or more halogen, SR4, OR3, COOR3, NR5R6, C1-C20heteroaryl, C1-C20heteroaryl-(CO)O, CONR5R6,
• or phenyl;
• or R22 is phenyl, naphthyl, coumarinyl or C1-C20heteroaryl, each of which optionally is substituted by one or more C1-C12alkyl, phenyl, halogen, C1-C4haloalkyl, CN, NO2, SR4, OR3, NR5R6 or by C3-C20cycloalkyl which optionally is interrupted by O, CO or NR5;
• or R22 is C2-C20alkanoyl, or benzoyl which is unsubstituted or substituted by one or more C1-C6alkyl, halogen, phenyl, SR4, OR3 or NR5R6;
• or R22 is C2-C12alkoxycarbonyl which optionally is interrupted by one or more O and/or optionally is substituted by one or more OH;
• or R22 is phenoxycarbonyl which is unsubstituted or substituted by one or more C1-C6alkyl, C1-C4haloalkyl, halogen, phenyl, SR4, OR3 or NR5R6;
• or R22 is NR5R6;
• or R22 forms a ring with one of the C-atoms of the phenyl ring to which the group
• is attached, wherein said formed ring is unsubstituted or substituted;
• R23 has one of the meanings as given for R1;
• and
• R24 is hydrogen, C1-C20alkyl, C1-C4haloalkyl, C2-C20alkyl which is interrupted by O, S or CO, or is phenyl-C1-C4alkyl, C3-C20cycloalkyl which optionally is interrupted by O, S or CO, or is phenyl.