Oxime derivatives and the use thereof as photoinitiators

A radically photopolymerizable composition comprising

• (a) at least one polymer or oligomer having at least two ethylenically unsaturated groups and at least one carboxyl function within the molecule structure;
• (b) as photoinitiator, at least one compound of the formula I, II, III, and IV
• m is 0 or 1;
• n is 0, 1, 2 or 3;
• x is 1 or 2;
• R1 is phenyl, phenyl which is substituted by one or more of the radicals C1-C12alkyl, C1-C4-haloalkyl, halogen, phenyl, OR10, NR11R12, SR13 and/or —S-phenyl, it being possible for the substituents OR10, SR13 and NR11R12 to form 5- or 6-membered rings, via the radicals R10, R11, R12 and/or R13, with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring,
• or R1 is naphthyl, anthracyl or phenanthryl, the radicals naphthyl, anthracyl and phenanthryl being unsubstituted or substituted by C1-C6alkyl, phenyl, OR10, NR11R12, SR13 and/or —S-phenyl, it being possible for the substituents OR10, SR13 and NR11R12 to form 5- or 6-membered rings, via the radicals R10, R11, R12 and/or R13 with further substituents on the naphthyl, anthracyl or phenanthryl ring or with one of the carbon atoms of the naphthyl, anthracyl or phenanthryl ring,
• or R1 is a heteroaryl radical which is unsubstituted or substituted by C1-C6alkyl, phenyl, OR10, NR11R12, SR13 and/or —S-phenyl, it being possible for the substituents OR10, SR13 and NR11R12 to form 5- or 6-membered rings, via the radicals R10, R11, R12 and/or R13 with further substituents on the heteroaryl ring or with one of the carbon atoms of the heteroaryl ring;
• or R1 is C2-C12alkenyl, C4-C8cycloalkenyl, or C6-C12bicycloalkenyl,
• or, if m is zero, R1 in the formula I additionally is benzoyl, 2-furoyl, 2-thiophenecarbonyl, 2-pyridinecarbonyl or 2-pyrrolecarbonyl, wherein the radicals benzoyl, 2-furoyl, 2-thiophenecarbonyl, 2-pyridinecarbonyl or 2-pyrrolecarbonyl are unsubstituted or substituted by one or more of the radicals C1-C12alkyl, C1-C4haloalkyl, halogen, phenyl, OR10, NR11R12, SR13 and/or —S-phenyl, it being possible for the substituents OR10, SR13 and NR11R12 to form 5- or 6-membered rings, via the radicals R10, R11, R12 and/or R13, with further substituents on the benzoyl, 2-furoyl, 2-thiophenecarbonyl, 2-pyridinecarbonyl or 2-pyrrolecarbonyl ring or with one of the carbon atoms of the benzoyl, 2-furoyl, 2-thiophenecarbonyl, 2-pyridinecarbonyl or 2-pyrrolecarbonyl ring;
• or, if m is zero, n is 1 and simultaneously R5 is phenyl which is unsubstituted or substituted by one or more C1-C12alkyl, C1-C4haloalkyl, halogen, phenyl, OR10, NR11R12, SR13 and/or —S-phenyl, R1 in formula I additionally is hydrogen;
• or, if m is 0 and n is 0, R1 in formual I additionally is CN, hydrogen or C1-C12 alkyl, with the proviso that R1 and R2 are not simultaneously hydrogen or alkyl;
• R′1 is C2-C12alkylene, phenylene, naphthylene,
• diphenylene or oxydiphenylene, these radicals are unsubstituted or substituted by C1-C12alkyl;
• R2 has one of the meanings of R1 or is phenyl, CN-substituted phenyl, C2-C6alkanoyl, benzoyl which is unsubstituted or substituted by C1-C6alkyl, phenyl, OR10, SR13, NR11R12 and/or —S-phenyl, or R2 is CN, phenoxycarbonyl, NO2, C1-C4haloalkyl, C2-C6alkoxycarbonyl, S(O)y—C1-C6alkyl, S(O)y—C6-C12aryl, C1-C12alkyl-substituted S(O)y—C6-C12aryl, SO2O—C1-C6alkyl, SO2O—C6-C10aryl, diphenylphosphinoyl or NHCONH2,
• or, if m is 1, R1 and R2 together with the CO group may form a 5- or 6-membered ring which is unsubstituted or substituted by C1-C6alkyl, phenyl, OR10, SR13, NR11R12 and/or —S-phenyl, said ring may additionally be interrupted by —O—, —S—, —N(R11)— and/or by CO, and to said ring may be fused one or more benzo radicals;
• y is 1 or 2;
• R3 if x is 1 is C1-C18alkylsulfonyl, phenyl-C1-C3alkylsulfonyl, camphorylsulfonyl, C1-C10haloalkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl, wherein the groups phenyl, naphthyl, anthracyl and phenanthryl of the radicals phenyl-C1-C3alkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl and phenanthrylsulfonyl are unsubstituted or substituted by one or more halogen, C1-C4haloalkyl, CN, NO2, C1-C16alkyl, phenyl, C1-C4alkylthio, OR10, COOR13, C1-C4alkyl-OCO—, R13OSO2— and/or —NR11R12;
• or R3 is C2-C6haloalkanoyl, halobenzoyl, or a group
• R3 if x is 2, is C2-C12alkylenedisulfonyl, phenylenedisulfonyl, naphthylenedisulfonyl,
• diphenylenedisulfonyl, or oxydiphenylenedisulfonyl, wherein the groups phenylene, naphthylene,
• diphenylene and oxydiphenylene of the radicals phenylenedisulfonyl, naphthylenedisulfonyl,
• diphenylenedisulfonyl, or oxydiphenylenedisulfonyl are unsubstituted or substituted by C1-C12alkyl;
• R4 and R5 are independently of each other hydrogen, halogen, C1-C8alkyl, C1-C6alkoxy, C1-C4haloalkyl, CN, NO2, C2-C6alkanoyl, benzoyl, phenyl, —S-phenyl, OR10, SR13, NR11R12, C2-C6alkoxycarbonyl, phenoxycarbonyl, S(O)yC1-C6alkyl, S(O)yC6-C12aryl, C1-C12alkyl-substituted S(O)yC6-C12aryl, SO2O—C1-C6alkyl, SO2O—C6-C10aryl or NHCONH2, or R4 and R5 together are a direct bond or —C(R21)═C(R22)—C(R23)═C(R24)—;
• A is —S—, —O—, —NR10—, or a group of formula A1, A2, A3 or A4
• Y, Y1, Y2 and Y3 independently of one another are —O— or —S—;
• Z is —CR28— or —N—;
• and
• Z1 is —CH2—, —S—, —O— or —NR10—;
• R10 is hydrogen, phenyl, C1-C12alkyl which is unsubstituted or substituted by phenyl, OH, C1-C12alkoxy, C1-C12alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or by C2-C6alkanoyl or R10 is C2-C12alkyl interrupted by one or more —O—, said interrupted C2-C12alkyl is unsubstituted or substituted by phenyl, OH, C1-C12alkoxy, C1-C12alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or by C2-C6alkanoyl;
• R11 and R12 independently of one another are hydrogen, C1-C12alkyl which is unsubstituted or substituted by OH, C1-C4alkoxy, C1-C12alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or C1-C6alkanoyl;
• or R11 and R12 are C2-C12alkyl interrupted by one or more —O—, said interrupted CC2-C12alkyl is unsubstituted or substituted by OH, C1-C4alkoxy, C1-C12alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or C1-C6alkanoyl;
• or R11 and R12 are phenyl, C2-C6alkanoyl, benzoyl, C1-C6alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl, or R11 and R12, together with the nitrogen atom to which they are bonded, form a 5-, 6- or 7-membered ring which may be interrupted by —O— or by —NR10—;
• R13 is C1-C12alkyl which is unsubstituted or substituted by OH and/or C1-C4alkoxy or R13 is C2-C12alkyl interrupted by one or more —O—, said interrupted C2-C12alkyl is unsubstituted or substituted by OH and/or C1-C4alkoxy;
• R14 and R15 independently of one another are C1-C6alkyl which is unsubstituted or substituted by halogen or phenyl or R14 and R15 are phenyl which is unsubstituted or substituted by C1-C4alkyl or halogen;
• R16 and R17 independently of one another have one of the meanings of R14, or R16 and R17 together are 1,2-phenylene or C2-C6alkylene which is unsubstituted or substituted by C1-C4alkyl or halogen;
• R18, R19 and R20 independently of each other are C1-C6alkyl which is unsubstituted or substituted by halogen;
• or R18, R19 and R20 are phenyl which is unsubstituted or substituted by C1-C4alkyl or halogen, or R19 and R20 together are 2,2′-biphenylene or C2-C6alkylene which is unsubstituted or substituted by C1-C4alkyl or halogen;
• R21, R22, R23 and R24 independently of each other are hydrogen, C1-C4alkyl, halogen, phenyl, OR10, SR13, NR11R12, —S-phenyl, C2-C6alkoxycarbonyl, phenoxycarbonyl, CN, NO2, C1-C4haloalkyl, S(O)yC1-C6alkyl, S(O)yC6-C12aryl, C1-C12alkyl-substituted S(O)yC6-C12aryl, SO2O—C1-C6alkyl, SO2O—C6-C10aryl or NHCONH2;
• R27 and R28 independently of one another have one of the meanings given for R4, or R27 and R28 together are —CO—NR10CO—, or —C(R21)═C(R22)—C(R23)═C(R24)—;
• and
• (c) at least one coinitiator.