Polymerizable compositions

A composition, comprising:

• (a) an ethylenically unsaturated, polymerizable monomer or oligomer;
• and
• (b) an effective, thermally or actinically radicals-generating amount of a compound of formula (I):
• wherein:
• Q is a direct bond or a bivalent radical —(CR8R9)—;
• Z1 is —O—, —NR10—, —CH2—, —(CR11R12)— or —C(═O)—;
• R1 and R2 are each, independently from the other, C1-C6ALKyl, or R1 and R2 are together C4-C7ALKylene thus forming a cyclic group with the C-atom to which they are attached;
• R3 and R4 are each, independently from the other, C1-C6ALKyl, or R3 and R4 are together C4-C7ALKylene thus forming a cyclic group with the C-atom to which they are attached;
• R5 and R6 are each, independently from the other, H, C1-C6ALKyl, C6-C10aryl or C7-C12arALKyl, or R5 and R6 are together oxygen thus forming a carbonyl group together with the C-atom to which they are attached;
• R7 is C6-C24aryl, C7-C24arALKyl, C1-C24heteroaryl or C2-C24heteroarALKyl;
• R8 and R9 are each, independently from the other, H or C1-C6ALKyl;
• R10 is hydrogen, C1-C6ALKyl, C6-C10aryl or —O—C(═O)—R13;
• R11 is hydrogen or C1-C6ALKyl;
• R12 is R14, C(═O)—R14, CN, OH, OR14, NH2, NHR14, NR14R15, O—C(═O)—R16, NH—C(═O)—R16 or NR14—C(═O)—R16;
• or R11 and R12 are together C2-C20ALKylene, which is uninterrupted or once or twice interrupted by —O— and/or —NR17— thus forming a ring with the C-atom to which they are attached, which C2-C20ALKylene can optionally be annelated with benzo or naphtho, and which C2-C20ALKylene is further unsubstituted or substituted by 1 or 2, identical or different, groups —OH or —O—C(═O)—R13;
• R13 is H, R18, OR18, NR18R19, COOR20, R21—COOR20 or R22(—COOR20)—COOR23;
• R14 and R15 are each, independently from the other, C1-C6ALKyl, C7-C12arALKyl or C6-C10aryl, or R14 and R15 are together C2-C6ALKylene, which is uninterrupted or once or twice interrupted by —O— and/or —NR17— thus forming a ring with the N-atom to which they are attached;
• R16 is H, R18, OR18, NR18R19, COOR20, R21—COOR20 or R22(—COOR20)—COOR23;
• R17 is H or C1-C6 ALKyl;
• R18 and R19 are each, independently from the other, C1-C36ALKyl, C2-C54ALKenyl, C2-C24ALKinyl, C6-C10aryl, C7-C46arALKyl or C2-C36ALKenylene-C6-C10aryl, or R18 and R19 are together C9-C36ALKylene or C2-C54ALKenylene, which is uninterrupted or once or twice interrupted by —O— and/or —NR17— thus forming a ring with the N-atom to which they are attached;
• R21 is C1-C12ALKylene, C2-C12ALKenylene, C2-C12ALKinylene, C6-C10arylene, C7-C18arALKylene or C2-C18ALKenylene-C6-C10arylene;
• R22 is C1-C12ALKantriyl, C2-C12ALKantriyl, benzotriyl, naphthotriyl, C7-C18-benzoALKantriyl, C11-C22naphthoALKantriyl, C2-C12ALKantriyl-C6-C10arylene, C2-C12ALKenylene-benzotriyl, C2-C12ALKenylene-naphthotriyl or C2-C12ALKentriyl-C6-C10arylene;
• each R20 or R23 stands, independently from any other R1, R2, R3, R4, R5, R6, R7, R11, R18, R19, R20 or R23, for H, R18, OR18, NR18R19, COOR20, R20—COOR20, R22(—COOR20)—COOR13 or
• ALK stands for a linear or once or several times branched, and/or mono- or polycyclic, hydrocarbon residue including spiro residues, wherein one or more —CH2— groups may be replaced by —S— or —NH—, one or more
• groups may be replaced by
• and/or one or more non-adjacent —CH2— groups may be replaced by —O—;
• each hydrocarbon residue, ALK, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R14, R15, R17, R18, R19, R21 and R22 is, independently from all others, unsubstituted or substituted by one or more identical or different substituents selected from the group consisting of Br, Cl, F, I, NO2, OR24, SR24, SCN, CN, N(R24)R25, N(R24)—C(═O)—R25, N(R24)—COOR25, N(COR24)COR25, COOR24,
• COO
• -
• ⁡
• [
• 1
• m
• ⁢
• M
• m
• +
• ]
• ,
• COR24, O—C(═O)R24, C(═O)NR24R25, O—C(═O)NR24R25,
• SO
• 3
• ⁢
• H
• ,
• SO
• 3
• -
• ⁡
• [
• 1
• m
• ⁢
• M
• m
• +
• ]
• ,
• SO2NR24R25, S(═O)R24, SO2R24 and P(═O)(OR24)OR25;
• R24 and R25 are each, independently from any other, H, C1-C18alkyl, C7-C18aralkyl, C6-C24aryl or C1-C24heteroaryl, or R24 and R25 are each, independently from any other, H, C1-C18alkyl, C7-C18aralkyl, C6-C24aryl or C1-C24heteroaryl and R24 and R25 are additionally bound together through a direct bond or bridged over a O, S, NH, N—C1-C18alkyl, N—C7-C18aralkyl, N—C6-C24aryl or N—C1-C24heteroaryl bridge;
• Mm+ is an organic or inorganic cation;
• m is 1, 2, 3 or 4;
• and
• n is 1, 2, 3 or 4, wherein the effective, thermally or actinically radicals-generating amount is such that from 0.01 to 30 triazene functional groups N—N═N—R7 are present in the compound (b) of formula (I) per 100 ethylenically unsaturated functional groups C═C of the polymerizable monomer or oligomer (a).