O-acyloxime photoinitiators

Details O-acyloxime photoinitiators O-acyloxime photoinitiators

1999-06-23

2003-07-22

McPherson, John A. (Department: 1756)

Radiation imagery chemistry: process, composition, or product th

Radiation modifying product or process of making

Screen other than for cathode-ray tube

C430S270100, C522S039000, C564S254000

Reexamination Certificate

active

06596445

ABSTRACT:

The invention pertains to new O-acyloxime compounds and their use as photoinitiators in photopolymerizable compositions.
From U.S. Pat. No. 3,558,309 it is known that certain oxime ester derivatives are photoinitiators. In U.S. Pat. No. 4,255,513 oxime ester compounds are disclosed. In U.S. Pat. No. 4,590,145 several p-dimethyl- and p-diethylamino-substituted oxime ester compounds are disclosed. U.S. Pat. No. 4,202,697 discloses acrylamino-substituted oxime esters. In Chemical Abstract No. 96:52526c, J. Chem. Eng. Data 9(3), 403-4 (1964), J. Chin. Chem. Soc. (Taipei) 41 (5) 573-8, (1994), JP 62-273259-A (=Chemical Abstract 109:83463w), JP 62-286961-A (=Derwent No. 88-025703/04), JP 62-201859-A (=Derwent No. 87-288481/41), JP 62-184056-A (=Derwent No. 87-266739/38), U.S. Pat. No. 5,019,482 and J. of Photochemistry and Photobiology A 107, 261-269 (1997) some p-alkoxy-phenyl oxime ester compounds are described.
In photopolymerization technology there still exists a need for highly reactive, easy to prepare and easy to handle photoinitiators. In addition, such new photoinitiators must meet the high requirements of the industry regarding properties like, for example, thermal stability and storage stability.
Surprisingly it was found, that compounds of the formulae I, II, III and IV
wherein
R
1
is phenyl which is unsubstituted or substituted by one or more C
1
-C
6
alkyl, phenyl, halogen, OR
8
, SR
9
or NR
10
R
11
; or R
1
is C
1
-C
20
alkyl or C
2
-C
20
alkyl optionally interrupted by one or more —O— and/or optionally substituted by one or more hydroxyl groups; or R
1
is C
5
-C
8
cycloalkyl, C
2
-C
2
oalkanoyl; or benzoyl which is unsubstituted or substituted by one or more C
1
-C
6
-alkyl, phenyl, OR
8
, SR
9
or NR
10
R
11
; or R
1
is C
2
-C
12
alkoxycarbonyl optionally interrupted by one or more —O— and/or optionally substituted by one or more hydroxyl groups; or R
1
is phenoxycarbonyl which is unsubstituted or substituted by C
1
-C
6
alkyl, halogen, phenyl, OR
8
or NR
10
R
11
; or R
1
is —CONR
10
R
11
, CN, NO
2
, C
1
-C
4
haloalkyl, S(O)
m
C
1
-C
6
alkyl; unsubstituted or C
1
-C
12
alkyl-substituted S(O)
m
—C
6
-C
12
aryl; SO
2
O—C
1
-C
6
alkyl, SO
2
O—C
6
-C
10
aryl, or diphenylphosphinoyl;
m is 1 or 2;
R
1
′ is C
2
-C
12
alkoxycarbonyl optionally interrupted by one or more —O— and/or optionally substituted by one or more hydroxyl groups; or R
1
′ is phenoxycarbonyl which is unsubstituted or substituted by one or more C
1
-C
6
alkyl, halogen, phenyl, OR
8
or NR
10
R
11
; or R
1
′ is C
5
-C
8
cycloalkyl, —CONR
10
OR
11
, CN; or phenyl which is substituted by SR
9
, wherein optionally a 5- or 6-membered ring is formed via the group R
9
by building a link to a carbon atom of the phenyl ring bearing the groups R
4
′, R
5
′ and R
6
′; or, if at least one of R
4
′, R
5
′ or R
6
′ is —SR
9
R
1
′ additionally is C
1
-C
12
alkyl which is unsubstituted or substituted by one or more halogen, OH, OR
2
, phenyl, halogenated phenyl or phenyl substituted by SR
9
, and which C
1
-C
12
alkyl otpionally is interrupted by —O— or —NH—(CO)—;
R
2
is C
2
-C
12
alkanoyl which is unsubstituted or substituted by one or more halogen or CN; or R
2
is C
4
-C
6
alkenoyl, provided that the double bond is not conjugated with the carbonyl group; or R
2
is benzoyl which is unsubstituted or substituted by one or more C
1
-C
6
alkyl, halogen, CN, OR
8
, SR
9
or NR
10
R
11
; or R
2
is C
2
-C
6
alkoxycarbonyl; or phenoxycarbonyl which is unsubstituted or substituted by C
1
-C
6
alkyl or halogen;
R
3
, R
4
, R
5
, R
6
and R
7
independently of one another are hydrogen, halogen, C
1
-C
12
alkyl, cyclopentyl, cyclohexyl; or phenyl which is unsubstituted or substituted by one or more OR
8
, SR
9
or NR
10
R
11
; or R
3
, R
4
, R
5
, R
6
and R
7
are benzyl, benzoyl, C
2
-C
12
alkanoyl; C
2
-C
12
-alkoxycarbonyl optionally interrupted by one or more —O— and/or optionally substituted by one or more hydroxyl groups; or R
3
, R
4
, R
5
, R
6
and R
7
are phenoxycarbonyl or a group OR
8
, SR
9
, SOR
9
, SO
2
R
9
or NR
10
R
11
, wherein the substituents OR
8
, SR
9
and NR
10
R
11
optionally form 5- or 6-membered rings via the radicals R
8
, R
9
, R
10
and/or R
11
with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring;
provided that at least one of the groups R
3
, R
4
, R
5
, R
6
or R
7
is OR
8
, SR
9
or NR
10
R
11
;
R
4
′, R
5
′ and R
6
′ independently of one another are hydrogen, halogen, C
1
-C
12
alkyl, cyclopentyl, cyclohexyl; phenyl which is unsubstituted or substituted by OR
8
, SR
9
or NR
10
R
11
; or R
4
′, R
5
′ and R
6
′ are benzyl, benzoyl, C
2
-C
12
alkanoyl; C
2
-C
12
alkoxycarbonyl optionally interrupted by one or more —O— and/or optionally substituted by one or more hydroxyl groups; or R
4
′, R
5
′ and R
6
′ are phenoxycarbonyl; or are a group OR
8
, SR
9
, SOR
9
, SO
2
R
9
, NR
10
R
11
, wherein the substituents OR
8
, SR
9
and NR
10
R
11
optionally form 5- or 6-membered rings via the radicals R
8
, R
9
, R
10
and/or R
11
with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring;
provided that at least one of R′
4
, R′
5
and R′
6
is OR
8
, SR
9
or NR
10
R
11
;
and provided that if R′
5
is methoxy and R′
4
and R′
6
are both simultaneously hydrogen and R′
1
is CN, R′
2
is not benzoyl or 4-(C
1
--C
10
alkyl)benzoyl;
R
8
is hydrogen, C
1
-C
12
alkyl; or C
2
-C
6
alkyl which is substituted by —OH, —SH, —CN, C
1
-C
4
-alkoxy, C
3
-C
6
alkenoxy, —OCH
2
CH
2
CN, —OCH
2
CH
2
(CO)O(C
1
-C
4
alkyl), —O(CO)—C
1
-C
4
alkyl, —O(CO)-phenyl, —(CO)OH or —(CO)O(C
1
-C
4
alkyl); or R
8
is C
2
-C
6
alkyl which is interrupted by one or more —O—; or R
8
is —(CH
2
CH
2
O)
n
H, C
2
-C
8
alkanoyl, C
3
-C
12
alkenyl, C
3
-C
6
alkenoyl, cyclohexyl; or phenyl which is unsubstituted or substituted by halogen, C
1
-C
12
alkyl or C
1
-C
4
alkoxy; or R
8
is phenyl-C
1
-C
3
alkyl, Si(C
1
-C
8
alkyl)r(phenyl)
3−r
, or a group
n is 1-20;
r is 1, 2 or 3;
R
9
is hydrogen, C
1
-C
12
alkyl, C
3
-C
12
alkenyl, cyclohexyl; C
2
-C
6
alkyl which is substituted by —OH, —SH, —CN, C
1
-C
4
alkoxy, C
3
-C
6
alkenoxy, —OCH
2
CH
2
CN, —OCH
2
CH
2
(CO)O(C
1
-C
4
alkyl), —O(CO)—C
1
-C
4
alkyl, —O(CO)-phenyl, —(CO)OH or —(CO)O(C
1
-C
4
alkyl); or R
9
is C
2
-C
12
alkyl which is interrupted by one or more —O— or —S—; or R
9
is phenyl which is unsubstituted or substituted by halogen, C
1
-C
12
alkyl or C
1
-C
4
alkoxy; or R
9
is phenyl-C
1
-C
3
alkyl or a group
R
10
and R
11
independently of each other are hydrogen, C
1
-C
12
alkyl, C
2
-C
4
hydroxyalkyl, C
2
-C
10
alkoxyalkyl, C
3
-C
5
alkenyl, C
5
-C
12
cycloalkyl, phenyl-C
1
-C
3
alkyl; phenyl which is unsubstituted or substituted by C
1
-C
12
alkyl or C
1
-C
4
alkoxy; or R
10
and R
11
are C
2
-C
3
alkanoyl, C
3
-C
6
-alkenoyl or benzoyl; or R
10
and R
11
together are C
2
-C
6
alkylene optionally interrupted by —O— or —NR
8
— and/or optionally substituted by hydroxyl, C
1
-C
4
alkoxy, C
2
-C
4
alkanoyloxy or benzoyloxy; or, when R
10
is hydrogen, R
11
may be a group of formula
M is C
1
-C
12
alkylene, cyclohexylene, phenylene, —(CO)O—(C
2
-C
12
alkylene)—O(CO)—, —(CO)O—(CH
2
CH
2
O)
n
—(CO)— or —(CO)—(C
2
-C
12
-alkylene)-(CO)—;
M
1
is a direct bond; or C
1
-C
12
alkyleneoxy-, optionally interrupted by 1 to 5 —O—, —S— and/or —NR
10
—;
M
2
is a direct bond; or C
1
-C
12
alkylene-S-, optionally interrupted by 1 to 5 —O—, —S— and/or —NR
10
—;
M
3
is a direct bond, a piperazino group; or C
1
-C
12
alkylene-NH— optionally interrupted by 1 to 5 —O—, —S— and/or —NR
10
—;
 provided that
(i) if R
5
is methoxy and R
2
is benzoyl or acetyl then R
1
is not phenyl;
(ii) if R
5
is methoxy and R
1
is ethoxycarbonyl, then R
2
is not benzoyl or ethoxycarbonyl;
(iii) if R
5
is methoxy and R
1
is 4-methoxybenzoyl, then R
2
is not ethoxycarbonyl;
(iv) if R
5
is methacryloylamino

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