Unsaturated oxime derivatives and the use thereof as latent...

Details Unsaturated oxime derivatives and the use thereof as latent... Unsaturated oxime derivatives and the use thereof as latent...

2001-02-15

2004-03-09

Baxter, Janet (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

C430S919000, C430S921000, C522S059000, C564S258000, C564S268000

Reexamination Certificate

active

06703182

ABSTRACT:

The invention relates to new unsaturated oxime derivatives, photopolymerisable compositions comprising said compounds and to the use of the compounds as latent acids, which can be activated by irradiation with light.
In U.S. Pat. No. 4,540,598 surface-coating compositions based on photosensitive oxime sulfonates and customary acid-curable resins are disclosed. In EP 571330 the use of &agr;-(4-toluene-sulfonyl-oxyimino)-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 wavelengths between 180 and 600 nm, especially those in the radiation region beyond 390 nm is reported. In U.S. Pat. No. 5,714,625 non aromatic &agr;-(alkylsulfonyloxyimino)-1-cyclohexenylacetonitriles and &agr;-(alkylsulfonyloxyimino)-1-cyclopentenylacetonitriles are disclosed. In Heterocycles, 38, 71 (1994), G. Nawwar et al. disclose 2-(p-tolylsulfonyloxyimino)-3-oxo-5-phenyl-pent-4-enenitrile as experimental product for investigations on a synthesis for pyrano-pyrroles.
In the art, a need still exists, especially for reactive non-ionic latent acid donors that are thermally and chemically stable and that, after being activated by light, can be used as catalysts for a variety of acid-catalysed reactions, such as polycondensation reactions, acid-catalysed depolymerisation reactions, acid-catalysed electrophilic substitution reactions or the acid-catalysed removal of protecting groups. There is also a need for compounds that when irradiated with light are converted into acids and are capable of acting as solubility inhibitors in resist formulations. Furthermore there is a need for photolatent acids which can be bleached upon irradiation.
Surprisingly, it has now been found that specific unsaturated oxime derivatives possessing at least one olefinically unsaturated double bond or triple bond which is conjugated with another olefinically unsaturated double bond or with an aromatic or heterocyclic double bond, are especially suitable as catalysts for such reactions. The optical absorption spectra of the specific compounds of the invention are particularly tunable over a wide range of the electromagnetic spectrum. Furthermore they can be bleached upon irradiation.
Accordingly, the present invention pertains to compounds of the formulae I, II or III
m is zero or 1;
n is 1, 2 or 3;
R
1
is phenyl, which is unsubstituted or substituted by one or more of the radicals C
1
-C
12
alkyl, C
1
-C
4
haloalkyl, halogen, phenyl, OR
6
, NR
7
R
8
, SR
9
and/or —S-phenyl, it being possible for the substituents OR
6
, SR
9
and NR
7
R
8
to form 5- or 6-membered rings, via the radicals R
6
, R
7
, R
8
and/or R
9
, 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, wherein the radicals naphthyl, anthracyl and phenanthryl are unsubstituted or substituted by C
1
-C
6
alkyl, phenyl, OR
6
, NR
7
R
8
, SR
9
and/or —S-phenyl, it being possible for the substituents OR
6
, SR
9
and NR
7
R
8
to form 5- or 6-membered rings, via the radicals R
6
, R
7
, R
8
and/or R
9
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
6
, NR
7
R
8
, SR
9
and/or —S-phenyl, it being possible for the substituents OR
6
, SR
9
and NR
7
R
8
to form 5- or 6-membered rings, via the radicals R
6
, R
7
, R
8
and/or R
9
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, with the proviso that the double bond (or the double bonds) of the radicals C
2
-C
12
alkenyl, C
4
-C
8
cycloalkenyl, or C
6
-C
12
bicycloalkenyl is (are) conjugated with the double bond substituted by R
4
and R
5
; or, if m is zero, R
1
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
6
, NR
7
R
8
, SR
9
and/or —S-phenyl, it being possible for the substituents OR
6
, SR
9
and NR
7
R
8
to form 5- or 6-membered rings, via the radicals R
6
, R
7
, R
8
and/or R
9
, 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
6
, NR
7
R
8
, SR
9
and/or —S-phenyl, R
1
additionally is hydrogen or halogen;
R′
1
is vinylene, phenylene, naphthylene,
 diphenylene or oxydiphenylene, wherein the radicals phenylene, naphthylene,
 diphenylene and oxydiphenylene are unsubstituted or substituted by C
1
-C
12
alkyl;
R
2
is CN, C
1
-C
4
haloalkyl, C
2
-C
6
alkoxycarbonyl, phenoxycarbonyl, C
1
-C
6
alkyl-S(O)
x
—, C
6
-C
12
aryl-S(O)x—, which is unsubstituted or substituted by C
1
-C
12
alkyl, or R
2
is C
1
-C
6
alkyl-SO
2
O—, C
6
-C
10
aryl-SO
2
O—, diphenyl-phosphinoyl or R
2
is benzoyl which is unsubstituted or substituted by CN, NO
2
or C
1
-C
4
haloalkyl;
x is 1 or 2;
R
3
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
6
, COOR
9
, C
1
-C
4
alkyl-OCO—, R
9
OSO
2
— and/or —NR
7
R
8
; or R
3
is C
2
-C
6
haloalkanoyl, halobenzoyl, triphenylsilyl, or a group
Y
1
, Y
2
and Y
3
are independently of each other O or S;
R′
3
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
haloalkyl, CN, NO
2
, C
2
-C
6
alkanoyl, benzoyl, phenyl, —S-phenyl, OR
6
, SR
9
, NR
7
R
8
, C
2
-C
6
alkoxycarbonyl or phenoxycarbonyl, or R
4
and R
5
together are a direct bond;
R
6
is hydrogen, phenyl, C
1
-C
12
alkyl which is unsubstituted or substituted by phenyl, OH, C
1
-C
12
alkoxy, C
1
-C
12
alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or by C
2
-C
6
alkanoyl, or R
6
is C
2
-C
12
alkyl which is interrupted by one or more —O— or —S—, wherein the interrupted C
2
-C
12
alkyl is unsubtstituted or substituted by phenyl, OH, C
1
-C
12
alkoxy, C
1
-C
12
alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or by C
2
-C
6
alkanoyl;
R
7
and R
8
are independently of each other hydrogen or C
1
-C
12
alkyl which is unsubstituted or substituted by OH, C
1
-C
4
alkoxy, C
1
-C
12
alkylsulfonyl, phenylsulfonyl, (4-methyl-phenyl)sulfonyl and/or C
1
-C
6
alkanoyl; or R
7
and R
8
are C
2
-C
12
alkyl which is interrupted by one or more —O—, wherein the —O-interrupted C
2
-C
12
alkyl is unsubtstituted or substituted by OH, C
1
-C
4
alkoxy, C
1
-C
12
alkylsul

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