Oxime derivatives and the use thereof as photoinitiators

Details Oxime derivatives and the use thereof as photoinitiators Oxime derivatives and the use thereof as photoinitiators

2001-08-27

2004-10-19

Ashton, Rosemary (Department: 1752)

Radiation imagery chemistry: process, composition, or product th

Imaging affecting physical property of radiation sensitive...

Radiation sensitive composition or product or process of making

C430S922000, C430S919000, C522S057000, C522S059000, C522S065000

Reexamination Certificate

active

06806024

ABSTRACT:

The invention relates to oxime derivatives and their use as photoinitiators in radically photopolymerizable compositions.
Oxime sulfonates are known as photoacid generators and accordingly are used in acid-curable compositions and in chemically amplified resists. In U.S. Pat. No. 4,540,598 surface-coating compositions based on photosensitive oxime sulfonates as photolatent acids and customary acid-curable resins are disclosed. In EP 571330 the use of &agr;-(4-toluene-sulfonyloxyimino)-4-methoxybenzyl cyanide and &agr;-(4-toluene-sulfonyloxyimino)-3-thienylmethyl cyanide as latent acid donors in positive and negative photoresists for wavelengths of 340-390 nm, especially those in the radiation region of the mercury i line (365 nm) is described. In GB 2306958 the use of oxime-sulfonates as latent acid donors in positive and negative photoresists for wave-lengths between 180 and 600 nm, especially those in the radiation region beyond 390 nm is reported. In U.S. Pat. No. 5714625 non-aromatic &agr;-(alkylsulfonyloxyimino)-1-cyclohexenylacetonitriles and &agr;-(alkylsulfonyloxyimino)-1-cyclopentenylacetonitriles are disclosed. It is known that certain oxime carboxylate ester derivatives are photoinitiators as described in U.S. Pat. No. 3,558,309. Further disclosure of oxime carboxylate ester compounds is given for example in U.S. Pat. Nos. 4,255,513, 4,590,145 , 4,202,697 , 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).
The use of hydroximic acid ester sulfonates as thermal initiators for the polymerization of olefines in a temperature range from 50-350° C. is described in EP 35291. The activation with light of these compounds is, however, not disclosed. Further, &agr;-oximinoacid ester sulfonates are mentioned as thermal acid generators for thermosetting coating compositions in EP 44115 and by W. J.-Mijis et al. in J. Coatings Technology 1983, 55, 45.
In radical photopolymerization technology there still exists a need for highly reactive, easy to prepare and easy to handle photoinitiator systems. 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 has now been found that specific oxime derivatives of the formulae I, II, III, IV, V and/or VI, as described below, are especially suitable as photoinitiators for radical photo-polymerization in combination with coinitiators.
In accordance with the invention, the compounds of the formulae I, II, III, IV, V and/or VI can be used as radical photoinitiators for the photopolymerization of ethylenically unsaturated compounds or of mixtures which comprise such compounds.
The invention therefore relates to a radically photopolymerizable composition comprising
(a) at least one ethylenically unsaturated photopolymerizable compound,
(b) as photoinitiator, at least one compound of the formula I, II, III, IV, V and/or VI
wherein
m is 0 or 1;
n is 0 , 1, 2 or 3;
x is 1 or 2;
R
1
is phenyl, phenyl which is substituted by one or more of the radicals C
1
-C
12
alkyl, C
1
-C
4
-haloalkyl, halogen, phenyl, OR
10
, NR
11
R
12
, SR
13
and/or —S-phenyl, it being possible for the substituents OR
10
, SR
13
and NR
11
R
12
to form 5- or 6-membered rings, via the radicals R
10
, R
11
, R
12
and/or R
13
, with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring,
or R
1
is naphthyl, anthracyl or phenanthryl, the radicals naphthyl, anthracyl and phenanthryl being unsubstituted or substituted by C
1
-C
6
alkyl, phenyl, OR
10
, NR
11
R
12
, SR
13
and/or —S-phenyl, it being possible for the substituents OR
10
, SR
13
and NR
11
R
12
to form 5- or 6-membered rings, via the radicals R
10
, R
11
, R
12
and /or R
13
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 R
1
is a heteroaryl radical which is unsubstituted or substituted by C
1
-C
6
alkyl, phenyl, OR
10
, NR
11
R
12
, SR
13
and/or —S-phenyl, it being possible for the substituents OR
10
, SR
13
and NR
11
R
12
to form 5- or 6-membered rings, via the radicals R
10
, R
11
, R
12
and/or R
13
with further substituents on the heteroaryl ring or with one of the carbon atoms of the heteroaryl ring; or
R
1
is C
2
-C
12
alkenyl, C
4
-C
8
cycloalkenyl, or C
6
-C
12
bicycloalkenyl,
or, if m is zero, R
1
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 C
1
-C
12
alkyl, C
1
-C
4
haloalkyl, halogen, phenyl, OR
10
, NR
11
R
12
, SR
13
and/or —S-phenyl, it being possible for the substituents OR
10
, SR
13
and NR
11
R
12
to form 5- or 6-membered rings, via the radicals R
10
, R
11
, R
12
and/or R
13
, 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 R
5
is phenyl which is unsubstituted or substituted by one or more C
1
-C
12
alkyl, C
1
-C
4
haloalkyl, halogen, phenyl, OR
10
, NR
11
R
12
, SR
13
and/or —S-phenyl, R
1
in formula I additionally is hydrogen;
or, if m is 0 and n is 0, R
1
in formual I additionally is CN, hydrogen or C
1
-C
12
alkyl, with the proviso that R
1
and R
2
are not simultaneously hydrogen or alkyl;
R′
1
is C
2
-C
12
alkylene, phenylene, naphthylene,
diphenylene or oxydiphenylene, these radicals are unsubstituted or substituted by C
1
-C
12
alkyl;
R
2
has one of the meanings of R
1
or is phenyl, CN-substituted phenyl, C
2
-C
6
alkanoyl, benzoyl which is unsubstituted or substituted by C
1
-C
6
alkyl, phenyl, OR
10
, SR
13
, NR
11
R
12
and/or —S-phenyl, or R
2
is CN, phenoxycarbonyl, NO
2
, C
1
-C
4
haloalkyl, C
2
-C
6
alkoxycarbonyl, S(O)
y
—C
1
-C
6
alkyl, S(O)
y
—C
6
-C
12
aryl, C
1
-C
12
alkyl-substituted S(O)
y
—C
6
-C
12
aryl, SO
2
O-C
1
-C
6
alkyl, SO
2
O-C
6
-C
10
aryl, diphenylphosphinoyl or NHCONH
2
,
or, if m is 1, R
1
and R
2
together with the CO group may form a 5- or 6-membered ring which is unsubstituted or substituted by C
1
-C
6
alkyl, phenyl, OR
10
, SR
13
, NR
11
R
12
and/or —S-phenyl, said ring may additionally be interrupted by —O—, —S—, —N(R
11
)— and/or by CO, and to said ring may be fused one or more benzo radicals;
y is 1 or 2;
R
3
if x is 1 is C
1
-C
18
alkylsulfonyl, phenyl-C
1
-C
3
alkylsulfonyl, camphorylsulfonyl, C
1
-C
10
haloalkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl, wherein the groups phenyl, naphthyl, anthracyl and phenanthryl of the radicals phenyl-C
1
-C
3
alkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl and phenanthrylsulfonyl are unsubstituted or substituted by one or more halogen, C
1
-C
4
haloalkyl, CN, NO
2
, C
1
-C
16
alkyl, phenyl, C
1
-C
4
alkylthio, OR
10
, COOR
13
, C
1
-C
4
alkyl-OCO—, R
13
OSO
2
— and/or —NR
11
R
12
; or R
3
is C
2
-C
6
haloalkanoyl, halobenzoyl, or a group
R
3
if x is 2, is C
2
-C
12
alkylenedisulfonyl, 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 C
1
-C
12
alkyl;
R
4
and R
5
are independently of each other hydrogen, halogen, C
1
-C
8
alkyl, C
1
-C
6
alkoxy, C
1
-C
4
hal

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