US 8,349,548 B2 · Oxime ester photoinitiators

Abstract

Compounds of the formula (I), wherein A1 is formula (II); A2 is formula (III); A3 is formula (IV); A4 is formula (V); w, x, y and z independently of each other are an integer from 0-4, provided that the sum of x+y+z is an integer from 2-4, corresponding to the valency of Q; M1, M2, M3 and M4 for example are a direct bond, CO or O; Y for example is a direct bond or S; Q is a (x+y)-valent linking group; R1 is for example hydrogen, C1-C20alkyl or phenyl or naphthyl; R2 and R″2 for example are is hydrogen or C1-C20alkyl; R3, R4, R′3, R′4, R″3 and R″4 for example are hydrogen, halogen, phenyl, or C1-C20alkyl; and R24 is for example a direct bond; exhibit an unexpectedly good performance in photopolymerization reactions.

Claims18

Dependent claims

A compound of the formula I

wherein
A1 is
A2 is
A3 is
A4 is
w, x, y and z independently of each other are an integer from 0-4, provided that the sum of w+x+y+z is an integer from 2-4, corresponding to the valency of Q;
and provided that, when more than one A1 or more than one A2 or more than one A3 or more than one A4 is present in the compound of the formula I, said multiple A1, multiple A2, multiple A3 and multiple A4 can be different from any other A1, A2, A3, or A4;
x is 0, 1 or 2;
y is 0, 1, 2 or 3;
z is 0 or 2;
w is 0 or 1;
M1 is no bond;
M2 and M3 independently of each other are no bond or a single bond;
M4 is CO;
Y is S;
Q is a C2-C10alkylene, S—C2-C10alkylene-S or S-alkanetriyl which is interrupted by CO and O;
R1 is C1-C4alkyl;
R2 is C1-C4alkyl or C1-C20heteroaryl;
R″2 is C1-C20heteroaryl;
R3, R4, R′3, R′4, R″3 and R″4 are hydrogen;
R5 is
or (CO)R15;
R15 is C1-C20heteroaryl;
R24 is a direct bond, phenylene, or phenylene-O;
provided that at least two oxime ester groups are present in at least one of the groups A1, A2, A3 or A4.

22 more elements

A photoinitiator mixture, comprising

(A) at least one compound of the formula I
wherein
A1 is
A2 is
A3 is
A4 is
w, x, y and z independently of each other are an integer from 0-4, provided that the sum of w+x+y+z is an integer from 2-4, corresponding to the valency of Q;
and provided that, when more than one A1 or more than one A2 or more than one A3 or more than one
A4 is present in the compound of the formula I, each A1, each A2, each A3 and each A4 can be different from any other A1, A2, A3, or A4;
M1, M2 and M3 independently of one another are no bond, a direct bond, CO, O, S, SO, SO2 or NR14;
provided that at least one of M1, M2 or M3 is a direct bond, CO, O, S, SO, SO2 or NR14;
M4 is a direct bond, CR3R4, CO, CS, O, S, SO, or SO2;
Y is a direct bond, S or NR18;
Q is a direct bond or a (w+x+y+z)-valent linking group;
R1 is hydrogen, C3-C8cycloalkyl, C2-C5alkenyl, C1-C20alkoxy or is unsubstituted or substituted C1-C20alkyl;
or R1 is phenyl or naphthyl, both of which are unsubstituted or substituted;
or R1 is benzyloxy or phenoxy both of which are unsubstituted or substituted;
R2 is hydrogen, C1-C20alkyl which C1-C20alkyl optionally contains one or more C—C multiple bonds and which is unsubstituted or substituted;
or R2 is C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14, and which uninterrupted or interrupted C3-C10cycloalkyl optionally contains one or more C—C multiple bonds;
or R2 is C2-C20alkyl interrupted by one or more O which interrupted C2-C20alkyl optionally contains C—C multiple bonds and is unsubstituted or substituted;
or R2 is phenyl, naphthyl, coumarinyl or C1-C20heteroaryl, each of which is unsubstituted or substituted;
or R2 is COR15 or COOR11;
or R2 is unsubstituted or substituted C2-C12alkoxycarbonyl optionally interrupted by one or more O and/or optionally substituted by one or more OH;
or R2 is unsubstituted or substituted phenoxycarbonyl;
or R2 is NR12R13,
or R2 forms a ring with one of the C-atoms of the phenyl or naphthyl ring to which the group
is attached, wherein said formed ring is unsubstituted or substituted;
R″2 has one of the meanings given for R2 or R″2 forms a ring with one of the C-atoms of the phenyl or naphthyl ring to which the group
is attached, wherein said formed ring is unsubstituted or substituted;
M5 is no bond, a direct bond, CO, O, S, SO, SO2 or NR14;
R3, R4, R′3, R′4, R″3 and R″4 independently of one another are hydrogen, halogen, unsubstituted or substituted phenyl, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by O, S, CO or NR14, or are C2-C12alkenyl, C2-C12alkenyl which is interrupted by O, S, CO or NR14, or are C4-C8cycloalkenyl, C2-C12alkinyl, unsubstituted or substituted phenyl-C1-C4alkyl, CN, NO2,
C3-C10 cycloalkyl or C3-C10cycloalkyl which is interrupted by O, S, CO or NR14;
or R3, R4, R′3, R′4, R″3 and R″4 are (CO)R15, SR10, OR11, SOR10, SO2R10 or NR12R13, wherein the substituents (CO)R15, OR11, SR10 and NR12R13 optionally form 5- or 6-membered rings via the radicals R10, R11, R12, R13, and/or R15 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring;
or R3 and R4, R′3 and R′4, R″3 and R″4 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 is unsubstituted or substituted, and wherein said bicyclic ring optionally is fused with further aromatic rings and/or heteroaromatic rings;
R5 is hydrogen, halogen, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by O, S, CO or NR14or is C3-C10cycloalkyl, C3-C10cycloalkyl which is interrupted by O, S, CO or NR14, or is C2-C12alkenyl, C2-C12alkenyl which is interrupted by O, CO or NR14, or is C4-C8cycloalkenyl, C2-C12alkinyl, unsubstituted or substituted phenyl, unsubstituted or substituted phenyl-C1-C4alkyl, CN, NO2,
or R5 is (CO)R15, SR10, OR11, SOR10, SO2R10 or NR12R13, wherein the substituents (CO)R15, OR11, SR10 and NR12R13 optionally form 5- or 6-membered rings via the radicals R10, R11, R12, R13 and/or R15 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring to which R5 is attached;
R6 and R′6 independently of one another are hydrogen, halogen, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by O, S, CO or NR14, or are C2-C12alkenyl, C2-C12alkenyl which is interrupted by O, S, CO or NR14, or are C4-C8cycloalkenyl, C2-C12alkinyl, unsubstituted or substituted phenyl-C1-C4alkyl, CN, NO2,
C3-C10cycloalkyl or C3-C10cycloalkyl which is interrupted by O, S, CO or NR14;
or R6 and R′6 are unsubstituted or substituted phenyl;
or R6 and R′6 are (CO)R15, SR10, OR11, SOR10, SO2R10 or NR12R13, wherein the substituents (CO)R15, OR11, SR10 and NR12R13 optionally form 5- or 6-membered rings via the radicals R10, R11, R12 R13, and/or R15 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring;
or R6 and R′6 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 is unsubstituted or substituted and wherein said bicyclic ring optionally is fused with further aromatic rings and/or heteroaromatic rings;
provided that the group
is attached to either ring of said bicyclic ring;
R7, R′7, R8 and R′8 independently of one another have one of the meanings as given for R3 and R4;
R9 and R′9 independently of one another are hydrogen, halogen, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by O, S, CO or NR14, or are C2-C12alkenyl which optionally is interrupted by O, S, CO or NR14, or are C4-C8cycloalkenyl, C2-C12alkinyl, unsubstituted or substituted phenyl-C1-C4alkyl, CN, NO2,
or C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14;
or R9 and R′9 are phenyl which is unsubstituted or substituted by one or more halogen, C1-C20alkyl, C1-C4haloalkyl, SR10, OR11 or NR12R13;
or R9 and R′9 are (CO)R15, SR10, OR11, SOR10, SO2R10 or NR12R13, wherein the substituents (CO)R15, OR11, SR10 and NR12R13 optionally form 5- or 6-membered rings via the radicals R10, R11, R12, R13, and/or R15 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring;
R10 is hydrogen, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by one or more O, S, CO or NR14;
or is C2-C12alkenyl, C10cycloalkyl which optionally is interrupted by O, S, CO or NR14, or R10 is unsubstituted or substituted phenyl-C1-C4alkyl;
or R10 is —(CH2CH2O)nH, —(CH2CH2O)n(CO)—(C1-C8alkyl), C2-C8alkanoyl, benzoyl, C3-C6alkenoyl;
or R10 is unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, or unsubstituted or substituted C1-C20heteroaryl, each of which is unsubstituted or substituted by one or more halogen, C1-C12alkyl, C1-C4haloalkyl, 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, unsubstituted or substituted C1-C20alkyl;
C2-C20alkyl which is interrupted by one or more O or S;
or is C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14;
or is unsubstituted or substituted phenyl-C1-C4-alkyl;
or R11 is benzoyl, phenyl, naphthyl or C1-C20heteroaryl each of which is unsubstituted or substituted;
or R11 forms a ring with one of the C-atoms of the group to which the group OR11 or COOR11 is attached, wherein said ring is unsubstituted or substituted;
R12 and R13 independently of one another are hydrogen, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by O, S, CO or NR14;
C2-C4hydroxyalkyl, C1-C12alkoxy, phenyl-C1-C4alkyl, (CO)R15, C2-C10alkoxyalkyl, C3-C5alkenyl, or C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14;
or R12 and R13 are unsubstituted or substituted phenyl or unsubstituted or substituted naphthyl;
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 unsubstituted or substituted ring, which ring optionally is interrupted by O, N, S, CO, or NR14;
or R12 and R13 together with the N-atom to which they are attached form a unsubstituted or substituted heteroaromatic ring system;
R14 is hydrogen, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by O, S or CO, or is unsubstituted or substituted phenyl-C1-C4alkyl, C3-C8cycloalkyl which optionally is interrupted by O, S or CO, or is (CO)R5 or is unsubstituted or substituted phenyl;
R15 is hydrogen, OH, unsubstituted or substituted C1-C20alkyl, C2-C20alkyl which interrupted by O, S, CO or NR14, C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14, or is unsubstituted or substituted phenyl-C1-C4alkyl, SR10, OR11 or NR12R13;
or R15 is phenyl, naphthyl, coumarinyl or C1-C20heteroaryl, each of which is unsubstituted or substituted;
R16 and R17 independently of each other are hydrogen, C1-C20alkyl, C1-C4haloalkyl, 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 is hydrogen, (CO)R2, C1-C20alkoxycarbonyl, unsubstituted or substituted phenyl-C1-C4alkyl, unsubstituted or substituted C1-C20alkyl;
or R18 is C2-C20alkyl which is interrupted by O, S, CO or NR14;
C2-C12alkenyl which optionally is interrupted by O, S, CO or NR14, or is C4-C8cycloalkenyl or C2-C12alkynyl;
or R18 is benzoyl, naphthoyl, phenyloxycarbonyl or naphthyloxycarbonyl each of which is unsubstituted or substituted;
or R18 is C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14, or is C3-C10cycloalkylcarbonyl which optionally is interrupted by O, S, CO or NR14, or is C3-C10cycloalkyloxycarbonyl which optionally is interrupted by O, S, CO or NR14;
or R18 is phenyl or naphthyl both of which are unsubstituted or substituted;
R20 is COOR11, CONR12R13, (CO)R1;
or R20 has one of the meanings as given for R12 and R13;
R21 is COOR11, CONR12R13, (CO)R1;
or R21 has one of the meanings as given for R15;
X is O, S, SO or SO2;
m is an integer 1 or 2;
R22 is hydrogen, C1-C20alkyl;
C2-C20alkenyl;
C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14, C3-C10cycloalkenyl;
unsubstituted or substituted C1-C20alkyl;
or R22 is unsubstituted or substituted C2-C20alkyl interrupted by one or more O;
or R22 is phenyl, naphthyl, coumarinyl or C1-C20heteroaryl, each of which is unsubstituted or substituted;
or R22 is C2-C20alkanoyl, or unsubstituted or substituted benzoyl;
or R22 is unsubstituted or substituted C2-C12alkoxycarbonyl optionally interrupted by one or more O;
or R22 is unsubstituted or substituted phenoxycarbonyl;
or R22 is NR12R13;
or R22 forms a ring with one of the C-atoms of the phenyl or naphthyl ring to which the group
is attached, wherein said formed ring is unsubstituted or substituted;
or R22 is
R23 has one of the meanings as given for R1;
R24 is a direct bond, C1-C20alkylene, which C1-C20alkylene optionally contains one or more C—C multiple bonds and which is unsubstituted or substituted;
or R24 is C3-C10cycloalkylene which optionally is interrupted by O, CO or NR14, and which uninterrupted or interrupted C3-C10cycloalkylene optionally contains one or more C—C multiple bonds;
or R24 is C2-C20alkylene interrupted by one or more O which interrupted C2-C20alkylene optionally contains C—C multiple bonds and is unsubstituted or substituted;
or R24 is phenylene, naphthylene, coumarinylene or C1-C20heteroarylene, each of which is unsubstituted or substituted;
or R24 is phenylene-O or naphthylene-O, each of which is unsubstituted or substituted;
or R24 is C1-C20alkylene-CO, or unsubstituted or substituted phenylene-CO;
or R24 is C1-C20alkylene-O—CO optionally interrupted by one or more O and/or optionally substituted by one or more OH;
or R24 are unsubstituted or substituted phenylene-O—CO;
NR12 or
(B) at least one compound of the formula I′
wherein
Q, A1, A2, A3, A4, R2, w, x, y and z are as defined hereinabove;
provided that at least one of the oxime groups
in the molecule is replaced by a group

112 more elements

A compound of the formula I′

wherein
A1 is
A2 is
A3 is
A4 is
w, x, y and z independently of each other are an integer from 0-4, provided that the sum of w+x+y+z is an integer from 2-4, corresponding to the valency of Q;
M1, M2 and M3 independently of one another are no bond, a direct bond, CO, O, S, SO, SO2 or NR14;
provided that at least one of M1, M2 or M3 is a direct bond, CO, O, S, SO, SO2 or NR14;
M4 is a direct bond, CR3R4, CO, CS, O, S, SO, or SO2;
Y is a direct bond, S or NR15;
Q is a direct bond or a (w+x+y+z)-valent linking group;
R1 is hydrogen, C3-C8cycloalkyl, C2-C5alkenyl, C1-C20alkoxy or is unsubstituted or substituted C1-C20alkyl;
or R1 is phenyl or naphthyl, both of which are unsubstituted or substituted;
or R1 is benzyloxy or phenoxy both of which are unsubstituted or substituted;
R2 is hydrogen, C1-C20alkyl which C1-C20alkyl optionally contains one or more C—C multiple bonds and which is unsubstituted or substituted;
or R2 is C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14, and which uninterrupted or interrupted C3-C10cycloalkyl optionally contains one or more C—C multiple bonds;
or R2 is C2-C20alkyl interrupted by one or more O which interrupted C2-C20alkyl optionally contains C—C multiple bonds and is unsubstituted or substituted;
or R2 is phenyl, naphthyl, coumarinyl or C1-C20heteroaryl, each of which is unsubstituted or substituted;
or R2 is COR15 or COOR11;
or R2 is unsubstituted or substituted C2-C12alkoxycarbonyl optionally interrupted by one or more O and/or optionally substituted by one or more OH;
or R2 is unsubstituted or substituted phenoxycarbonyl;
or R2 is NR12R13,
or R2 forms a ring with one of the C-atoms of the phenyl or naphthyl ring to which the group
is attached, wherein said formed ring is unsubstituted or substituted;
R″2 has one of the meanings given for R2,
or R″2 forms a ring with one of the C-atoms of the phenyl or naphthyl ring to which the group
is attached, wherein said formed ring is unsubstituted or substituted;
M5 is no bond, a direct bond, CO, O, S, SO, SO2 or NR14;
R3, R4, R′3, R′4, R″3 and R″4 independently of one another are hydrogen, halogen, unsubstituted or substituted phenyl, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by O, S, CO or NR14, or are C2-C12alkenyl, C2-C12alkenyl which is interrupted by O, S, CO or NR14, or are C4-C8cycloalkenyl, C2-C12alkinyl, unsubstituted or substituted phenyl-C1-C4alkyl, CN, NO2,
C3-C10cycloalkyl or C3-C10cycloalkyl which is interrupted by O, S, CO or NR14;
or R3, R4, R′3, R′4, R″3 and R″4 are (CO)R15, SR10, OR11, SOR10, SO2R10 or NR12R13, wherein the substituents (CO)R15, OR11, SR10 and NR12R13 optionally form 5- or 6-membered rings via the radicals R10, R11, R12 R13, and/or R15 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring;
or R3 and R4, R′3 and R′4, R″3 and R″4 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 is unsubstituted or substituted, and wherein said bicyclic ring optionally is fused with further aromatic rings and/or heteroaromatic rings;
R5 is hydrogen, halogen, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by O, S, CO or NR14, or is C3-C10cycloalkyl, C3-C10cycloalkyl which is interrupted by O, S, CO or NR14, or is C2-C12alkenyl, C2-C12alkenyl which is interrupted by O, CO or NR14, or is C4-C8cycloalkenyl, C2-C12alkinyl, unsubstituted or substituted phenyl, unsubstituted or substituted phenyl-C1-C4alkyl, CN, NO2,
or R5 is (CO)R15, SR10, OR11, SOR10, SO2R10 or NR12R13, wherein the substituents (CO)R15, OR11, SR10 and NR12R13 optionally form 5- or 6-membered rings via the radicals R10, R11, R12 R13 and/or R15 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring to which R5 is attached;
R6 and R′6 independently of one another are hydrogen, halogen, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by O, S, CO or NR14, or are C2-C12alkenyl, C2-C12alkenyl which is interrupted by O, S, CO or NR14, or are C4-C8cycloalkenyl, C2-C12alkinyl, unsubstituted or substituted phenyl-C1-C4alkyl, CN, NO2,
C3-C10cycloalkyl or C3-C10cycloalkyl which is interrupted by O, S, CO or NR14;
R6 and R′6 are unsubstituted or substituted phenyl;
or R6 and R′6 are (CO)R15, SR10, OR11, SOR10, SO2R10 or NR12R13, wherein the substituents (CO)R15, OR11, SR10 and NR12R13 optionally form 5- or 6-membered rings via the radicals R10, R11, R12 R13, and/or R15 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring;
or R6 and R′6 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 is unsubstituted or substituted and wherein said bicyclic ring optionally is fused with further aromatic rings and/or heteroaromatic rings;
provided that the group is
attached to either ring of said bicyclic ring;
R7, R′7, R8 and R′8 independently of one another have one of the meanings as given for R3 and R4;
R9 and R′9 independently of one another are hydrogen, halogen, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by O, S, CO or NR14, or are C2-C12alkenyl which optionally is interrupted by O, S, CO or NR14, or are C4-C8cycloalkenyl, C2-C12alkinyl, unsubstituted or substituted phenyl-C1-C4alkyl, CN, NO2,
or C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14;
or R9 and R′9 are phenyl which is unsubstituted or substituted by one or more halogen, C1-C20alkyl, C1-C4haloalkyl, SR10, OR11 or NR12R13;
or R9 and R′9 are (CO)R15, SR10, OR11, SOR10, SO2R10 or NR12R13, wherein the substituents (CO)R15, OR11, SR10 and NR12R13 optionally form 5- or 6-membered rings via the radicals R10, R11, R12R13, and/or R15 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring;
R10 is hydrogen, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by one or more O, S, CO or NR14;
or is C2-C12alkenyl, C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14, or R10 is unsubstituted or substituted phenyl-C1-C4alkyl;
or R10 is —(CH2CH2O)nH, —(CH2CH2O)n(CO)—(C1-C8alkyl), C2-C8alkanoyl, benzoyl, C3-C6alkenoyl;
or R10 is unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, or unsubstituted or substituted C1-C20heteroaryl, each of which is unsubstituted or substituted by one or more halogen, C1-C12alkyl, C1-C4haloalkyl, 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, unsubstituted or substituted C1-C20alkyl;
C2-C20alkyl which is interrupted by one or more O or S;
or is C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14;
or is unsubstituted or substituted phenyl-C1-C4-alkyl;
or R11 is benzoyl, phenyl, naphthyl or C1-C20heteroaryl each of which is unsubstituted or substituted;
or R11 forms a ring with one of the C-atoms of the group to which the group OR11 or COOR11 is attached, wherein said ring is unsubstituted or substituted;
R12 and R13 independently of one another are hydrogen, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by O, S, CO or NR14;
C2-C4hydroxyalkyl, C1-C12alkoxy, phenyl-C1-C4alkyl, (CO)R15, C2-C10alkoxyalkyl, C3-C5alkenyl, or C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14;
or R12 and R13 are unsubstituted or substituted phenyl or unsubstituted or substituted naphthyl;
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 unsubstituted or substituted ring, which ring optionally is interrupted by O, N, S, CO, or NR14;
or R12 and R13 together with the N-atom to which they are attached form a unsubstituted or substituted heteroaromatic ring system;
R14 is hydrogen, unsubstituted or substituted C1-C20alkyl, unsubstituted or substituted C2-C20alkyl which is interrupted by O, S or CO, or is unsubstituted or substituted phenyl-C1-C4alkyl, C3-C8cycloalkyl which optionally is interrupted by O, S or CO, or is (CO)R15 or is unsubstituted or substituted phenyl;
R15 is hydrogen, OH, unsubstituted or substituted C1-C20alkyl, C2-C20alkyl which interrupted by O, S, CO or NR14, C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14, or is unsubstituted or substituted phenyl-C1-C4alkyl, SR10, OR11 or NR12R13;
or R15 is phenyl, naphthyl, coumarinyl or C1-C20heteroaryl, each of which is unsubstituted or substituted;
R16 and R17 independently of each other are hydrogen, C1-C20alkyl, C1-C4haloalkyl, 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 is hydrogen, (CO)R2, C1-C20alkoxycarbonyl, unsubstituted or substituted phenyl-C1-C4alkyl, unsubstituted or substituted C1-C20alkyl;
or R18 is C2-C20alkyl which is interrupted by O, S, CO or NR14;
C2-C12alkenyl which optionally is interrupted by O, S, CO or NR14, or is C4-C8cycloalkenyl or C2-C12alkynyl;
or R18 is benzoyl, naphthoyl, phenyloxycarbonyl or naphthyloxycarbonyl each of which is unsubstituted or substituted;
or R18 is C3-C10cycloalkyl which optionally is interrupted by O, S, CO or NR14, or is C3-C10cycloalkylcarbonyl which optionally is interrupted by O, S, CO or NR14, or is C3-C10cycloalkyloxycarbonyl which optionally is interrupted by O, S, CO or NR14;
or R18 is phenyl or naphthyl both of which are unsubstituted or substituted;
R20 is COOR11, CONR12R13, (CO)R1;
or R20 has one of the meanings as given for R12 and R13;
R21 is COOR11, CONR12R13, (CO)R1;
or R21 has one of the meanings as given for R15;
X is O, S, SO or SO2;
m is an integer 1 or 2;
R22 is hydrogen, C1-C20alkyl;
C2-C20alkenyl;
C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14, C3-C10cycloalkenyl;
unsubstituted or substituted C1-C20alkyl;
or R22 is unsubstituted or substituted C2-C20alkyl interrupted by one or more O or R22 is phenyl, naphthyl, coumarinyl or C1-C20heteroaryl, each of which is unsubstituted or substituted;
or R22 is C2-C20alkanoyl, or unsubstituted or substituted benzoyl;
or R22 is unsubstituted or substituted C2-C12alkoxycarbonyl optionally interrupted by one or more O;
or R22 is unsubstituted or substituted phenoxycarbonyl;
or R22 is NR12R13;
or R22 forms a ring with one of the C-atoms of the phenyl or naphthyl ring to which the group
is attached, wherein said formed ring is unsubstituted or substituted;
or R22 is
R23 has one of the meanings as given for R1;
R24 is a direct bond, C1-C20alkylene, which C1-C20alkylene optionally contains one or more C—C multiple bonds and which is unsubstituted or substituted;
or R24 is C3-C10cycloalkylene which optionally is interrupted by O, CO or NR14, and which uninterrupted or interrupted C3-C10cycloalkylene optionally contains one or more C—C multiple bonds;
or R24 is C2-C20alkylene interrupted by one or more O which interrupted C2-C20alkylene optionally contains C—C multiple bonds and is unsubstituted or substituted;
or R24 is phenylene, naphthylene, coumarinylene or C1-C20heteroarylene, each of which is unsubstituted or substituted;
or R24 is phenylene-O or naphthylene-O, each of which is unsubstituted or substituted;
or R24 is C1-C20alkylene-CO, or unsubstituted or substituted phenylene-CO;
or R24 is C1-C20alkylene-O—CO optionally interrupted by one or more O and/or optionally substituted by one or more OH;
or R24 are unsubstituted or substituted phenylene-O—CO;
NR12 or
provided that at least one of the oxime groups
in the molecule is replaced by a group

106 more elements

Dependencies are inferred from the claim text.

Oxime ester photoinitiators

Life of this patent

Oxime ester photoinitiators

Life of this patent

Abstract

Claims18