U.S. patent application number 11/999116 was filed with the patent office on 2008-11-20 for sulfonate derivatives and the use thereof as latent acids.
Invention is credited to Toshikage Asakura, Akira Matsumoto, Peter Murer, Hitoshi Yamato.
Application Number | 20080286693 11/999116 |
Document ID | / |
Family ID | 27675790 |
Filed Date | 2008-11-20 |
United States Patent
Application |
20080286693 |
Kind Code |
A1 |
Matsumoto; Akira ; et
al. |
November 20, 2008 |
Sulfonate derivatives and the use thereof as latent acids
Abstract
Chemically amplified photoresist compositions comprising, (a) a
compound which cures upon the action of an acid or a compound whose
solubility is increased upon the action of an acid; and (b) a
compound of the formula Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va,
Vb or VIa ##STR00001## ##STR00002## wherein n is 1 or 2; m is 0 or
1; X.sub.0 is --[CH.sub.2].sub.h--X or --CH.dbd.CH.sub.2; h is 2,
3, 4, 5 or 6; R.sub.1, when n is 1, is for example optionally
substituted phenyl, naphthyl, anthracyl, phenanthryl, or
heteroaryl; R.sub.1, when n is 2, is for example optionally
substituted phenylene or naphthylene; R.sub.2 for example has one
of the meanings of R.sub.1; X is for example --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23; X' is --X.sub.1-A.sub.3-X-;
X.sub.1 and X.sub.2 are for example --O--, --S-- or a direct bond;
A.sub.3 is e.g. phenylene; R.sub.3 has for example one of the
meanings given for R.sub.1; R.sub.4 has for example one of the
meaning given for R.sub.2; R.sub.5 and R.sub.6 e.g. are hydrogen; G
i.a. is --S-- or --O--; R.sub.7 when n is 1, e.g. is phenyl,
optionally substituted, when n is 2, is for example phenylene;
R.sub.8 and R.sub.9 e.g. are C.sub.1-C.sub.18alkyl; R.sub.10 has
one of the meanings given for R.sub.7; R.sub.11 i.a. is
C.sub.1-C.sub.18alkyl; R.sub.12, R.sub.13, R.sub.14, R.sub.15
R.sub.16, R.sub.17 and R.sub.18 for example are hydrogen or
C.sub.1-C.sub.18alkyl; R.sub.20, R.sub.21, R.sub.22 and R.sub.23
i.a. are phenyl or C.sub.1-C.sub.18alkyl; give high resolution with
good resist profile.
Inventors: |
Matsumoto; Akira; (Basel,
CH) ; Yamato; Hitoshi; (Takarazuka-shi, JP) ;
Asakura; Toshikage; (Osaka, JP) ; Murer; Peter;
(Allschwil, CH) |
Correspondence
Address: |
JoAnn Villamizar;Ciba Corporation/Patent Department
540 White Plains Road, P.O. Box 2005
Tarrytown
NY
10591
US
|
Family ID: |
27675790 |
Appl. No.: |
11/999116 |
Filed: |
December 4, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10495710 |
Jul 30, 2004 |
7326511 |
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PCT/EP03/00821 |
Jan 28, 2003 |
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11999116 |
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Current U.S.
Class: |
430/288.1 ;
430/281.1 |
Current CPC
Class: |
G03F 7/038 20130101;
G03F 7/0392 20130101; Y10S 430/114 20130101; G03F 7/001 20130101;
G03F 7/0397 20130101; C07C 323/66 20130101; G03F 7/0758 20130101;
G03F 7/0045 20130101; C07C 381/00 20130101; B33Y 70/00 20141201;
G03F 7/0382 20130101; G03F 7/0037 20130101 |
Class at
Publication: |
430/288.1 ;
430/281.1 |
International
Class: |
G03F 7/20 20060101
G03F007/20 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 6, 2002 |
EP |
02405082.5 |
Claims
1. A compound of the formula Ia, Ib, IIa, IIb, IIIa, IIIb, IVa,
IVb, Va, Vb or VIa ##STR00074## ##STR00075## n is 1 or 2; m is 0 or
1; X.sub.0 is --[CH.sub.2].sub.h--X or --CH.dbd.CH.sub.2; h is 2,
3, 4, 5 or 6; R.sub.1 when n is 1, is phenyl, naphthyl, anthracyl,
phenanthryl, or heteroaryl, all of which are optionally substituted
by one or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or are substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19 form 5-, 6- or 7-membered rings, via the
radicals R.sub.19, R.sub.20, R.sub.21, R.sub.22 and/or R.sub.23,
with further substituents on the phenyl, naphthyl, anthracyl,
phenanthryl, or heteroaryl ring or with one of the carbon atoms of
the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring;
or R.sub.1 is hydrogen, with the proviso that R.sub.2 is not
simultaneously hydrogen; or R.sub.1 is C.sub.1-C.sub.18alkyl; or is
C.sub.2-C.sub.18alkyl which is interrupted by one or more
C.sub.3-C.sub.30cycloalkylene, --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, --S(CO)--, --NR.sub.23(CO)--, --SO--,
--SO.sub.2--, or --OSO.sub.2--; optionally the radicals
C.sub.1-C.sub.18alkyl and C.sub.2-C.sub.18alkyl are substituted by
one or more C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl,
halogen, --NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.1 is
C.sub.3-C.sub.30cycloalkyl, optionally interrupted by one or more
--O--, --S--, --NR.sub.23--, --(CO)--, --O(CO)--, or
--NR.sub.23(CO)--, and which is unsubstituted or substituted by one
or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.1 is C.sub.1-C.sub.8haloalkyl,
C.sub.2-C.sub.12alkenyl, C.sub.4-C.sub.30cycloalkenyl, camphoryl;
or if m is 0, R.sub.1 additionally is CN,
C.sub.2-C.sub.6alkoxycarbonyl or phenoxycarbonyl, wherein
C.sub.2-C.sub.6alkoxycarbonyl and phenoxycarbonyl optionally are
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl;
C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; or
are substituted by halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; R.sub.1, when n is 2, is phenylene,
naphthylene, ##STR00076## diphenylene, oxydiphenylene or
##STR00077## wherein these radicals are unsubstituted or
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, or R.sub.1 is a direct bond ##STR00078##
wherein all radicals R.sub.1 with the exception of hydrogen and
direct bond can additionally be substituted by a group having a
--O--C-bond or a --O--Si-bond which cleaves upon the action of an
acid; A.sub.1 is a direct bond, C.sub.1-C.sub.18alkylene, --O--,
--S--, --NR.sub.23--, --O(CO)--, --S(CO)--, --NR.sub.23(CO)--,
--SO--, --SO.sub.2-- or --OSO.sub.2--; A.sub.2 is a direct bond,
C.sub.1-C.sub.18alkylene; or is C.sub.2-C.sub.18alkylene which is
interrupted by one or more C.sub.3-C.sub.30cycloalkylene, --O--,
--S--, --NR.sub.23--, --(CO)--, --O(CO)--, --S(CO)--,
--NR.sub.23(CO)--, --SO--, --SO.sub.2--, --OSO.sub.2-- or
--Ar.sub.2--; optionally the radicals C.sub.1-C.sub.18alkylene and
C.sub.2-C.sub.18alkylene are substituted by one or more
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or A.sub.2 is C.sub.3-C.sub.30cycloalkylene,
optionally interrupted by one or more --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, or --NR.sub.23(CO)--, and which is
unsubstituted or substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or A.sub.2 is phenylene, naphthylene, wherein
these radicals optionally are substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; R.sub.2 has one of the meanings of
R.sub.1 or is C.sub.2-C.sub.18alkanoyl; benzoyl that is
unsubstituted or substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.2 is NO.sub.2; or R.sub.2 is
S(O).sub.pC.sub.1-C.sub.18alkyl, S(O).sub.p--C.sub.6-C.sub.12aryl,
SO.sub.2O--C.sub.1-C.sub.18alkyl, SO.sub.2O--C.sub.6-C.sub.10aryl,
diphenyl-phosphinoyl, all of which optionally are substituted by
one or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or are substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.1 and R.sub.2 together form a 5-, 6-
or 7-membered ring which is unsubstituted or substituted by one or
more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or is substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; and said 5-, 6- or 7-membered ring may
additionally be interrupted by C.sub.1-18alkylene,
C.sub.3-C.sub.30cycloalkylene, C.sub.1-C.sub.8haloalkylene,
C.sub.2-C.sub.12alkenylene, C.sub.4-C.sub.30cycloalkenylene,
phenylene, naphthalene, --O--, --S--, --NR.sub.23--, --(CO)--,
--O(CO)--, --NR.sub.23(CO)--, --S(CO)--, --SO--, --SO.sub.2--, or
--OSO.sub.2--, and to said 5-, 6- or 7-membered ring optionally are
fused one or more benzo radicals; p is 1 or 2; X is
--O(CO)R.sub.24, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.24, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19,
--OSO.sub.2R.sub.19, or the groups ##STR00079## X' is
-X.sub.1-A.sub.3-X.sub.2-; X.sub.1 and X.sub.2 independently of
each other are --O(CO)--, --O(CO)O--, --O(CO)NR.sub.23--,
--NR.sub.23(CO)--, --NR.sub.23(CO)O--, --O--, --NR.sub.23--, --S--,
--SO--, --SO.sub.2--, --OSO.sub.2--, ##STR00080## or X.sub.1 and
X.sub.2 are a direct bond, with the proviso that X.sub.1 and
X.sub.2 are not both simultaneously a direct bond; A3 is phenylene,
naphthylene, ##STR00081## diphenylene, oxydiphenylene or
##STR00082## wherein these radicals are unsubstituted or
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, or A.sub.3 is a direct bond, ##STR00083##
R.sub.3 has one of the meanings given for R.sub.1; or R.sub.3 is
C.sub.2-C.sub.18alkanoyl; benzoyl which optionally is substituted
by one or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.3 is NO.sub.2; or R.sub.3 is
S(O).sub.pC.sub.1-C.sub.18alkyl, S(O).sub.p--C.sub.6-C.sub.12aryl,
SO.sub.2O--C.sub.1-C.sub.18alkyl, SO.sub.2O--C.sub.6-C.sub.10aryl,
diphenyl-phosphinoyl, all of which optionally are substituted by
one or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or is substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; R.sub.4 has one of the meaning given for
R.sub.2, or R.sub.3 and R.sub.4 together form a 5-, 6- or
7-membered ring which optionally is substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or said 5-, 6- or 7-membered ring is
substituted by halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; and said 5-, 6- or 7-membered ring
optionally additionally is interrupted by C.sub.1-18alkylene,
C.sub.3-C.sub.30cycloalkylene, C.sub.1-C.sub.8haloalkylene,
C.sub.2-C.sub.12alkenylene, C.sub.4-C.sub.30cycloalkenylene,
phenylene, naphthalene, --O--, --S--, --NR.sub.23--, --(CO)--,
--O(CO)--, --NR.sub.23(CO)--, --S(CO)--, --SO--, --SO.sub.2--, or
--OSO.sub.2--; and optionally one or more benzo radicals are fused
to said 5-, 6- or 7-membered ring; R.sub.5 and R.sub.6
independently of each other are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl;
C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; or
R.sub.5 and R.sub.6 are halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.5 and R.sub.6 together are
--C(R.sub.30).dbd.C(R.sub.31)--C(R.sub.32).dbd.C(R.sub.33)-- or
--(CO)NR.sub.23(CO)--; G is --S--, --O--, --NR.sub.23--, or a group
of formula Z.sub.1, Z.sub.2, Z.sub.3 or Z ##STR00084## R.sub.7 when
n is 1, is phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl,
all of optionally are substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--
or --NR.sub.23(CO)--; or are substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19 form 5-, 6- or 7-membered rings, via the
radicals R.sub.19, R.sub.20, R.sub.21, R.sub.22 and/or R.sub.23,
with further substituents on the phenyl, naphthyl, anthracyl,
phenanthryl, or heteroaryl ring or with one of the carbon atoms of
the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring;
or R.sub.7 is C.sub.1-C.sub.18alkyl; or is C.sub.2-C.sub.18alkyl
which is interrupted by one or more
C.sub.3-C.sub.30cycloalkylene,
--O--, --S--, --NR.sub.23--, --(CO)--, --O(CO)--, --S(CO)--,
--NR.sub.23(CO)--, --SO--, --SO.sub.2--, or --OSO.sub.2--;
optionally the radicals C.sub.1-C.sub.18alkyl and
C.sub.2-C.sub.18alkyl are substituted by one or more
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.7 is C.sub.3-C.sub.30cycloalkyl,
optionally interrupted by one or more --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, or --NR.sub.23(CO)--, and optionally
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.7 is hydrogen,
C.sub.1-C.sub.8haloalkyl, --OR.sub.20, --NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --SR.sub.23, C.sub.2-C.sub.12alkenyl,
C.sub.4-C.sub.30cycloalkenyl, camphoryl; and R.sub.7, when n is 2,
is phenylene, naphthylene, ##STR00085## diphenylene, oxydiphenylene
or ##STR00086## wherein these radicals are optionally substituted
by one or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19, or R.sub.7 is a direct bond,
##STR00087## wherein all radicals R.sub.7 with the exception of
hydrogen and direct bond optionally additionally are substituted by
a group having a --O--C-bond or a --O--Si-bond which cleaves upon
the action of an acid; A4 is a direct bond,
C.sub.1-C.sub.18alkylene, --O--, --S-- or --NR.sub.23--; R.sub.8
and R.sub.9 independently of each other are C.sub.1-C.sub.18alkyl;
or are C.sub.2-C.sub.18alkyl which is interrupted by one or more
C.sub.3-C.sub.30cycloalkylene, --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, --S(CO)--, --NR.sub.23(CO)--, --SO--,
--SO.sub.2--, --OSO.sub.2-- or --Ar.sub.2--; optionally the
radicals C.sub.1-C.sub.18alkyl and C.sub.2-C.sub.18alkyl are
substituted by one or more C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.8 and R.sub.9 are
C.sub.3-C.sub.30cycloalkyl, optionally interrupted by one or more
--O--, --S--, --NR.sub.23--, --(CO)--, --O(CO)--, or
--NR.sub.23(CO)--, and optionally substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.8 and R.sub.9 are hydrogen,
halogen, C.sub.1-C.sub.8haloalkyl, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.8 and R.sub.9, if appropriate,
together with C.sub.1-C.sub.4alkylene, --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, --NR.sub.23(CO)-- form a 5-, 6-, or 7-membered
ring; or R.sub.7 and R.sub.8, if appropriate, together with
C.sub.1-C.sub.3alkylene, --O--, --S--, --NR.sub.23--, --(CO)--,
--O(CO)--, --NR.sub.23(CO)-- form a 5-, 6-, or 7-membered ring;
R.sub.10 has one of the meanings given for R.sub.7; R.sub.11 is
C.sub.1-C.sub.18alkyl; or C.sub.2-C.sub.18alkyl which is
interrupted by one or more C.sub.3-C.sub.30cycloalkylene, --O--,
--S--, --NR.sub.23--, --(CO)--, --O(CO)--, --S(CO)--,
--NR.sub.23(CO)--, --SO--, --SO.sub.2--, --OSO.sub.2-- or
--Ar.sub.2--; optionally the radicals C.sub.1-C.sub.18alkyl and
C.sub.2-C.sub.18alkyl are substituted by one or more
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.11 is C.sub.3-C.sub.30cycloalkyl,
optionally interrupted by one or more --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, or --NR.sub.23(CO)--, and optionally
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.11 is hydrogen,
C.sub.1-C.sub.8haloalkyl, --Ar.sub.1, --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22 or --SO.sub.2R.sub.19; or
R.sub.10 and R.sub.11 together form a 5-, 6- or 7-membered ring
which optionally is substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or said 5-, 6- or 7-membered ring is
substituted by halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; and said 5-, 6- or 7-membered ring
optionally additionally is interrupted by C.sub.1-C.sub.12alkylene,
C.sub.3-C.sub.30cycloalkylene, C.sub.1-C.sub.8haloalkylene,
C.sub.2-C.sub.12alkenylene, C.sub.4-C.sub.30cycloalkenylene,
phenylene, naphthalene, --O--, --S--, --NR.sub.23--, --(CO)--,
--O(CO)--, --NR.sub.23(CO)--, --S(CO)--, --SO--, --SO.sub.2--, or
--OSO.sub.2--; and to said 5-, 6- or 7-membered ring optionally are
fused one or more benzo radicals; with the provisos that, (1) if h
is 2, X' is -X.sub.1-A3-X.sub.2- and X.sub.1, X.sub.2 and A.sub.3
all are a direct bond, then R.sub.10 and R.sub.11 do not form a
ring interrupted by --CO--; (2) if X.sub.0 is --CH.dbd.CH.sub.2 and
R.sub.11 is methyl, then R.sub.10 is not phenyl or naphthyl; and
(3) if X.sub.0 is --CH.dbd.CH.sub.2 or if X.sub.0 is
--[CH.sub.2].sub.h--X, X is OR.sub.20 and R.sub.20 is methyl, then
R.sub.10 and R.sub.11, together do not form 5-, 6- or 7-membered
rings which are interrupted by --CO--; R.sub.12, R.sub.13, R.sub.14
and R.sub.15 independently of each other are hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or R.sub.12, R.sub.13, R.sub.14 and R.sub.15
are halogen, --NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; optionally the substituents R.sub.12,
R.sub.13, R.sub.14 and/or R.sub.15 form 5-, 6- or 7-membered rings
or fused rings, via the radicals R.sub.12, R.sub.13, R.sub.14
and/or R.sub.15 with further substituents on the phenyl to which
R.sub.12, R.sub.13, R.sub.14 and R.sub.15 are bonded, or with one
of the carbon atoms of said phenyl ring; wherein all radicals
radicals R.sub.12, R.sub.13, R.sub.14 and/or R.sub.15 with the
exception of hydrogen optionally additionally are substituted by a
group having a --O--C-bond or a --O--Si-bond which cleaves upon the
action of an acid; R.sub.16, R.sub.17 and R.sub.18 independently of
each other are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl;
C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; or
R.sub.16, R.sub.17 and R.sub.18 are halogen, --NO.sub.2, --CN,
--Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents R.sub.16,
R.sub.17, and/or R.sub.18 form 5-, 6- or 7-membered rings or fused
rings, via the radicals R.sub.16, R.sub.17, and/or R.sub.18 with
further substituents on the phenyl ring to which R.sub.16, R.sub.17
and R.sub.18 are bonded or with one of the carbon atoms of said
phenyl ring; wherein all radicals radicals R.sub.16, R.sub.17,
and/or R.sub.18 with the exception of hydrogen optionally
additionally are substituted by a group having a --O--C-bond or a
--O--Si-bond which cleaves upon the action of an acid; with the
proviso that (4) R.sub.16, R.sub.17 and R.sub.18 are not all
simultaneously hydrogen, if X.sub.0 is --CH.dbd.CH.sub.2; R.sub.19
is phenyl, naphthyl, C.sub.3-C.sub.30cycloalkyl,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.2-C.sub.12alkenyl, C.sub.4-C.sub.30cycloalkenyl; or is
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--; or
is C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; all
of which optionally are substituted by one or more Ar.sub.1, OH,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.19 is hydrogen; R.sub.20 is phenyl,
naphthyl, C.sub.3-C.sub.30cycloalkyl, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.12alkenyl,
C.sub.4-C.sub.30cycloalkenyl; or is C.sub.2-C.sub.18alkyl which is
interrupted by one or more --O--; or is C.sub.3-C.sub.30cycloalkyl
which is interrupted by one or more --O--, --S--, --NR.sub.23--,
--O(CO)-- or --NR.sub.23(CO)--; or is C.sub.2-C.sub.18alkanoyl, or
is benzoyl, or is C.sub.1-C.sub.18alkylsulfonyl, all of which
optionally are substituted by one or more Ar.sub.1, OH,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.20 is hydrogen, phenylsulfonyl,
(4-methylphenyl)sulfonyl, naphthylsulfonyl, anthracylsulfonyl or
phenanthrylsulfonyl; R.sub.21, R.sub.22 and R.sub.23 independently
of each other are phenyl, naphthyl, C.sub.3-C.sub.30cycloalkyl,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.2-C.sub.12alkenyl, C.sub.4-C.sub.30cycloalkenyl; or are
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--; or
are C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; or
are C.sub.2-C.sub.18alkanoyl, benzoyl or
C.sub.1-C.sub.18alkylsulfonyl, all of which optionally are
substituted by one or more Ar.sub.1, OH, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl,
phenylthio, phenylthiocarbonyl, --NR.sub.21R.sub.22,
C.sub.1-C.sub.12alkylthio, C.sub.2-C.sub.12alkoxycarbonyl,
C.sub.2-C.sub.8haloalkanoyl, halobenzoyl,
C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkyl-sulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.21, R.sub.22 and R.sub.23
independently of each other are hydrogen, phenylsulfonyl,
(4-methyl-phenyl)sulfonyl, naphthylsulfonyl, anthracylsulfonyl or
phenanthrylsulfonyl; or R.sub.21 and R.sub.22, together with the
nitrogen atom to which they are attached, form a 5-, 6- or
7-membered ring which optionally is interrupted by --O-- or by
--NR.sub.23--; with the provisos that (5) if m is 1, X.sub.0 is
--[CH.sub.2].sub.h--X, X is OR.sub.20 or NR.sub.21R.sub.22 and
R.sub.20 is hydrogen, or R.sub.2, and R.sub.22 both are hydrogen,
then R.sub.1 and R.sub.2 are not both simultaneously p-tolyl or
p-chlorophenyl; (6) if m is 0, X.sub.0 is --[CH.sub.2].sub.h--X, X
is NR.sub.21R.sub.22 and R.sub.2, and R.sub.22 both are the same
and are alkyl, which is interrupted by 0, then R.sub.1 is not
thienyl; (7) if X.sub.0 is --[CH.sub.2].sub.h--X, X is OR.sub.20,
R.sub.20 is ethyl and R.sub.8 and R.sub.9 both are hydrogen, then
R.sub.7 is not propyl; (8) if X.sub.0 is --CH.dbd.CH.sub.2, R.sub.8
and R.sub.9 both are hydrogen, n is 1, R.sub.7 is NR.sub.21R.sub.22
and R.sub.21 is hydrogen, then R.sub.22 is not n-C.sub.3H.sub.7,
i-C.sub.3H.sub.7 or cyclohexyl and R.sub.21 and R.sub.22 are not
both simultaneously alkenyl; R.sub.24 is phenyl, naphthyl,
C.sub.3-C.sub.30cycloalkyl, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.4-C.sub.30cycloalkenyl; or is
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--, or
is C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; all
of which are unsubstituted or substituted by one or more Ar
.sub.1, OH, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8-haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8halo-alkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.24 is hydrogen; or R.sub.23 and
R.sub.24 together with the N-atom to which they are attached form a
5-, 6- or 7-membered ring which optionally is interrupted by --CO--
or --O-- and which additionally optionally is fused with one or
more benzo rings; R.sub.25, R.sub.26 and R.sub.27 independently of
each other are hydrogen; or are phenyl or naphthyl, both of which
optionally are substituted by one or more Ar.sub.1, OH,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkyl-sulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.25, R.sub.26 and R.sub.27 are
C.sub.3-C.sub.18alkenyl or C.sub.3-C.sub.18alkynyl; or R.sub.25,
R.sub.26 and R.sub.27 are C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--,
and wherein the radicals C.sub.1-C.sub.18alkyl and
C.sub.2-C.sub.18alkyl are optionally substituted by one or more
Ar.sub.1, OH, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.25 and R.sub.26, if appropriate
together with C.sub.1-C.sub.2alkylene, --O--, --S--, or --CO--,
form a fused ring; or R.sub.25, R.sub.26 and R.sub.27, if
appropriate together with C.sub.1-C.sub.2alkylene, --O--, --S--, or
--CO--, form a 5-, 6-, or 7-membered ring; or R.sub.25, R.sub.26
and R.sub.27 together with the N.sup.+-atom to which they are
bonded form a group ##STR00088## R.sub.28 and R.sub.29
independently of each other are phenyl which optionally is
substituted by one or more Ar.sub.1, OH, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl,
phenylthio, phenylthiocarbonyl, --NR.sub.21R.sub.22,
C.sub.1-C.sub.12alkylthio, C.sub.2-C.sub.12alkoxycarbonyl,
C.sub.2-C.sub.8haloalkanoyl, halobenzoyl,
C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.28 and R.sub.29 independently of
each other are C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkyl which
is interrupted by one or more --O--, and wherein the radicals
C.sub.1-C.sub.18alkyl and C.sub.2-C.sub.18alkyl are optionally
substituted by one or more Ar.sub.1, OH, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl,
phenylthio, phenylthiocarbonyl, --NR.sub.21R.sub.22,
C.sub.1-C.sub.12alkylthio, C.sub.2-C.sub.12alkoxycarbonyl,
C.sub.2-C.sub.8haloalkanoyl, halobenzoyl,
C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.28 and R.sub.29, if appropriate
together with C.sub.1-C.sub.2alkylene, --O--, --S--, or --CO--,
form a fused ring; or R.sub.28 and R.sub.29, if appropriate
together with C.sub.1-C.sub.2alkylene, --O--, --S--, or --CO--,
form a 5-, 6- or 7-membered ring; R.sub.30, R.sub.31, R.sub.32 and
R.sub.33 are independently of each other hydrogen, halogen,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkoxy,
C.sub.1-C.sub.8haloalkyl, CN, NO.sub.2, C.sub.2-C.sub.18alkanoyl,
benzoyl, phenyl, --S-phenyl, OR.sub.20, SR.sub.23,
NR.sub.21R.sub.22, C.sub.2-C.sub.6alkoxycarbonyl, phenoxycarbonyl,
S(O).sub.pC.sub.1-C.sub.18alkyl, unsubstituted or
C.sub.1-C.sub.18alkyl-substituted S(O).sub.p--C.sub.6-C.sub.12aryl,
SO.sub.2O--C.sub.1-C.sub.18alkyl, SO.sub.2O--C.sub.6-C.sub.10aryl
or NHCONH.sub.2; R.sub.34 and R.sub.35 independently of each other
have one of the meanings given for R.sub.5; or R.sub.34 and
R.sub.35 together are --CO--NR.sub.23CO--; or R.sub.34 and R.sub.35
together are
--C(R.sub.30).dbd.C(R.sub.31)--C(R.sub.32).dbd.C(R.sub.33)--;
Ar.sub.1 is phenyl, naphthyl, anthracyl, phenanthryl, or
heteroaryl, all of which optionally are substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or are substituted by halogen, --NO.sub.2,
--CN, phenyl, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19 form 5-, 6- or 7-membered rings, via the
radicals R.sub.19, R.sub.20, R.sub.21, R.sub.22 and/or R.sub.23,
with further substituents on the phenyl, naphthyl, anthracyl,
phenanthryl, or heteroaryl ring or with one of the carbon atoms of
the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring;
Ar.sub.2 is phenylene, naphthylene, ##STR00089## diphenylene,
oxydiphenylene or ##STR00090## wherein these radicals optionally
are substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19 form 5-, 6- or 7-membered rings, via the
radicals R.sub.19, R.sub.20, R.sub.21, R.sub.22 and/or R.sub.23,
with further substituents on these radicals or with one of the
carbon atoms of these radicals; M.sup.+ is ##STR00091## Li.sup.+,
Na.sup.+, K.sup.+, Cs.sup.+, 1/2Mg.sup.2+, 1/2Ca.sup.2+ or
1/2Ba.sup.2+; L.sup.- is F.sup.-, Cl.sup.-, Br.sup.-, I.sup.-,
HSO.sub.4.sup.-, 1/2SO.sub.4.sup.2-, NO.sub.3.sup.-, ##STR00092##
ClO.sub.4.sup.-, BF.sub.4.sup.-, PF.sub.6.sup.-, AsF.sub.6.sup.-,
SbF.sub.6.sup.-(R.sub.50SO.sub.2).sub.3C.sup.- or
(R.sub.50SO.sub.2).sub.2N.sup.-; R.sub.36, R.sub.37, R.sub.38 and
R.sub.39 have one of the meanings given for R.sub.25, R.sub.26 and
R.sub.27; R.sub.40, R.sub.41 and R.sub.42 have one of the meanings
given for R.sub.28 and R.sub.29; R.sub.43 and R.sub.44
independently of each other are phenyl, which optionally is
substituted by one or more Ar.sub.1, OH, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl,
phenylthio, phenylthiocarbonyl, --NR.sub.21R.sub.22,
C.sub.1-C.sub.12alkylthio, C.sub.2-C.sub.12alkoxycarbonyl,
C.sub.2-C.sub.8haloalkanoyl, halobenzoyl,
C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.43 and R.sub.44, if appropriate
together with C.sub.1-C.sub.2alkylene, --O--, --S--, or --CO--,
form a fused ring; R.sub.45 is C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, camphoryl, phenyl-C.sub.1-C.sub.3alkyl,
C.sub.3-C.sub.30cycloalkyl, C.sub.4-C.sub.30cycloalkenyl, phenyl,
naphthyl, anthracyl or phenanthryl; all of which optionally are
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; R.sub.46 and R.sub.47 independently of one
another have one of the meanings given for R.sub.5; or R.sub.46 and
R.sub.47 together are --CO--NR.sub.23--CO-- or
--C(R.sub.30).dbd.C(R.sub.31)--C(R.sub.32).dbd.C(R.sub.33)--;
R.sub.48 and R.sub.49 independently of one another have on of the
meanings given for R.sub.5, or R.sub.48 and R.sub.49 together are
--CO--NR.sub.23--CO-- or
--C(R.sub.30).dbd.C(R.sub.31)--C(R.sub.32).dbd.C(R.sub.33)--;
R.sub.50 is C.sub.1-C.sub.8-perfluoroalkyl; Q.sub.1 is
--CR.sub.35-- or --N--; and Q.sub.2 is --CH.sub.2--, --S--, --O--
or --NR.sub.23--.
2. A compound of the formula Ia, Ib, IIa or IIb according to claim
1.
3. A compound of the formula Ia, Ib, IIa or IIb according to claim
1, wherein m is 0; R.sub.2 is C.sub.1-C.sub.8haloalkyl or --CN;
R.sub.4 is --CN; G is --S-- or a group of formula Z.sub.1.
4. A composition comprising (a) a compound which cures upon the
action of an acid or a compound whose solubility is increased upon
the action of an acid; and (b) as photosensitive acid donor, at
least one compound of the formula Ia, Ib, IIa, IIb, IIIa, IIIb,
IVa, IVb, Va, Vb or VIa according to claim 1.
Description
[0001] This application is a divisional of U.S. application Ser.
No. 10/495,710, filed on Jul. 30, 2004 which is a national stage
application of International Application No. EP 03/00821, filed on
Jan. 28, 2003, both herein incorporated entirely by reference.
[0002] The invention relates to new sulfonate derivatives,
chemically amplified photoresist compositions comprising said
compounds and to the use of the compounds as latent acids, which
can be activated by irradiation with actinic electromagnetic
radiation and electron beams.
[0003] In GB 2348644, WO 99/01429, EP 571330, JP 09-95479, and EP
768572, oxime sulfonate compounds are described as photolatent acid
generators for chemically amplified resists. In DE 4236068 and DE
4139419, .alpha.-sulfonyloxy carbonyl compounds are described as
photolatent acid generators for chemically amplified resists. In JP
2000-330282, JP 2000-89459 and JP 11-352677, N-sulfonyloxyimide
compounds are described as photolatent acid generators for
chemically amplified resists. In EP 631188 and EP 717319,
o-nitrobenzyl-sulfonate compounds are described as photolatent acid
generators for chemically amplified resists. In JP 9-127697,
pyrogallol sulfonates compounds are described as photolatent acid
generators for chemically amplified resists. In JP 04-198939, U.S.
Pat. No. 5,624,777, U.S. Pat. No. 5,714,289, U.S. Pat. No.
5,116,710, JP 07-84379 and JP 11-202483,
2-[methacryloyloxy]ethanesulfonate compounds,
3-[methacryloyloxy]propanesulfonate compounds and
4-[methacryloyloxy]butane-sulfonate compounds are described as
monomer of one component of a polymer for electrophotographic
lithographic plates. In JP 10-221852,
3-[methacryloyloxy]propanesulfonate compounds are described as
monomer of one component of a polymer for a positive tone
photoresist. In U.S. Pat. No. 4,736,055,
2-[acryloyloxy]ethanesulfonyloxyimino-benzoyl-phenylmethane,
2-[methacryloylamino]ethanesulfonyloxyimino-diphenylmethane,
2-[3-[methacryloyloxy]-2-hydroxypropanesulfonyloxyimino]-hexanoic
acid, methyl ester,
2-hydroxyethanesulfonyloxyimino-[4'-chlorobenzoyl]-[4''-chlorophenyl]meth-
ane, and
2-aminoethanesulfonyloxyimino-[4'-methylbenzoyl]-[4''-methylpheny-
l]methane are described as oxime sulfonate compounds containing
reactive groups which can react with polymer or with precursors and
the use of the resultant polymers for the photochemical production
of images are described.
[0004] In the art exists a need for reactive non-ionic latent acid
donors that are thermally and chemically stable and that, after
being activated by light, UV-radiation, X-ray irradiation or
electron beams can be used as catalysts for a variety of
acid-catalysed reactions, such as poly-condensation reactions,
acid-catalysed depolymerisation reactions, acid-catalysed
electro-philic substitution reactions or the acid-catalysed removal
of protecting groups. A particular need exists for latent acid
catalysts with high stability and good solubility and to such which
give high resolution with good resist profile in the field of
chemically amplified photoresists.
[0005] Surprisingly, it has now been found that specific sulfonate
derivatives, as described below, are especially suitable as
catalysts for the aforementioned acid catalyzed reactions. By
irradiation with actinic electromagnetic radiation and electron
beams, sulfonate derivatives in the present invention release less
diffusable acid in the resist formulation, leading to high
resolution with a good resist profile. The optical absorption
spectra of the specific compounds of the invention are tunable over
a wide range of the electromagnetic spectrum and particularly
suitable for applications in the deep UV range. Furthermore,
chemically amplified photoresist compositions comprising sulfonate
derivatives of the present invention are thermally stable, even at
high bake temperatures during processing and provide high
photospeed.
[0006] The invention accordingly relates to a chemically amplified
photoresist composition comprising
(a) a compound which cures upon the action of an acid or a compound
whose solubility is increased upon the action of an acid; and (b)
as photosensitive acid donor, at least one compound of the formula
Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa
##STR00003## ##STR00004##
n is 1 or 2; m is 0 or 1; X.sub.0 is --[CH.sub.2].sub.h--X or
--CH.dbd.CH.sub.2; h is 2, 3, 4, 5 or 6; R.sub.1 when n is 1, is
phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl, all of
which are optionally substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or are substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19 form 5-, 6- or 7-membered rings, via the
radicals R.sub.19, R.sub.20, R.sub.21, R.sub.22 and/or R.sub.23,
with further substituents on the phenyl, naphthyl, anthracyl,
phenanthryl, or heteroaryl ring or with one of the carbon atoms of
the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring;
or R.sub.1 is hydrogen, with the proviso that R.sub.2 is not
simultaneously hydrogen; or R.sub.1 is C.sub.1-C.sub.18alkyl; or is
C.sub.2-C.sub.18alkyl which is interrupted by one or more
C.sub.3-C.sub.30cycloalkylene, --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, --S(CO)--, --NR.sub.23(CO)--, --SO--,
--SO.sub.2--, or --OSO.sub.2--; optionally the radicals
C.sub.1-C.sub.18alkyl and C.sub.2-C.sub.18alkyl are substituted by
one or more C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl,
halogen, --NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.1 is
C.sub.3-C.sub.30cycloalkyl, optionally interrupted by one or more
--O--, --S--, --NR.sub.23--, --(CO)--, --O(CO)--, or
--NR.sub.23(CO)--, and which is unsubstituted or substituted by one
or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.1 is C.sub.1-C.sub.8haloalkyl,
C.sub.2-C.sub.12alkenyl, C.sub.4-C.sub.30cycloalkenyl, camphoryl;
or if m is 0, R.sub.1 additionally is CN,
C.sub.2-C.sub.6alkoxycarbonyl or phenoxycarbonyl, wherein
C.sub.2-C.sub.6alkoxycarbonyl and phenoxycarbonyl optionally are
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl;
C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; or
are substituted by halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; R.sub.1, when n is 2, is phenylene,
naphthylene,
##STR00005##
diphenylene, oxydiphenylene or
##STR00006##
wherein these radicals are unsubstituted or substituted by one or
more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19, or R.sub.1 is a direct bond
##STR00007##
wherein all radicals R.sub.1 with the exception of hydrogen and
direct bond can additionally be substituted by a group having a
--O--C-bond or a --O--Si-bond which cleaves upon the action of an
acid; A.sub.1 is a direct bond, C.sub.1-C.sub.18alkylene, --O--,
--S--, --NR.sub.23--, --O(CO)--, --S(CO)--, --NR.sub.23(CO)--,
--SO--, --SO.sub.2-- or --OSO.sub.2--; A.sub.2 is a direct bond,
C.sub.1-C.sub.18alkylene; or is C.sub.2-C.sub.18alkylene which is
interrupted by one or more C.sub.3-C.sub.30cycloalkylene, --O--,
--S--, --NR.sub.23--, --(CO)--, --O(CO)--, --S(CO)--,
--NR.sub.23(CO)--, --SO--, --SO.sub.2--, --OSO.sub.2-- or
--Ar.sub.2--; optionally the radicals C.sub.1-C.sub.18alkylene and
C.sub.2-C.sub.18alkylene are substituted by one or more
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or A.sub.2 is C.sub.3-C.sub.30cycloalkylene,
optionally interrupted by one or more --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, or --NR.sub.23(CO)--, and which is
unsubstituted or substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or A.sub.2 is phenylene, naphthylene, wherein
these radicals optionally are substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; R.sub.2 has one of the meanings of
R.sub.1 or is C.sub.2-C.sub.18alkanoyl; benzoyl that is
unsubstituted or substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.2 is NO.sub.2; or R.sub.2 is
S(O).sub.pC.sub.1-C.sub.18alkyl, S(O).sub.p--C.sub.6-C.sub.12aryl,
SO.sub.2O--C.sub.1-C.sub.18alkyl, SO.sub.2O--C.sub.6-C.sub.10aryl,
diphenyl-phosphinoyl, all of which optionally are substituted by
one or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or are substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.1 and R.sub.2 together form a 5-, 6-
or 7-membered ring which is unsubstituted or substituted by one or
more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or is substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; and said 5-, 6- or 7-membered ring may
additionally be interrupted by C.sub.1-C.sub.8alkylene,
C.sub.3-C.sub.30cycloalkylene, C.sub.1-C.sub.8haloalkylene,
C.sub.2-C.sub.12alkenylene, C.sub.4-C.sub.30cycloalkenylene,
phenylene, naphthalene, --O--, --S--, --NR.sub.23--, --(CO)--,
--O(CO)--, --NR.sub.23(CO)--, --S(CO)--, --SO--, --SO.sub.2--, or
--OSO.sub.2--, and to said 5-, 6- or 7-membered ring optionally are
fused one or more benzo radicals; p is 1 or 2; X is
--O(CO)R.sub.24, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.24, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19,
--OSO.sub.2R.sub.19, or the groups
##STR00008##
X' is -X.sub.1-A.sub.3-X.sub.2
[0007] X.sub.1 and X.sub.2 independently of each other are
--O(CO)--, --O(CO)O--, --O(CO)NR.sub.23--, --NR.sub.23(CO)--,
--NR.sub.23(CO)O--, --O--, --NR.sub.23--, --S--, --SO--,
--SO.sub.2--, --OSO.sub.2--,
##STR00009##
or X.sub.1 and X.sub.2 are a direct bond, with the proviso that
X.sub.1 and X.sub.2 are not both simultaneously a direct bond;
A.sub.3 is phenylene, naphthylene,
##STR00010##
diphenylene, oxydiphenylene or
##STR00011##
wherein these radicals are unsubstituted or substituted by one or
more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19, or A.sub.3 is a direct bond,
##STR00012##
R.sub.3 has one of the meanings given for R.sub.1; or R.sub.3 is
C.sub.2-C.sub.18alkanoyl; benzoyl which optionally is substituted
by one or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.3 is NO.sub.2; or R.sub.3 is
S(O).sub.pC.sub.1-C.sub.18alkyl, S(O)p--C.sub.6-C.sub.12aryl,
SO.sub.2O--C.sub.1-C.sub.18alkyl, SO.sub.2O--C.sub.6-C.sub.10aryl,
diphenyl-phosphinoyl, all of which optionally are substituted by
one or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or is substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; R.sub.4 has one of the meaning given for
R.sub.2, or R.sub.3 and R.sub.4 together form a 5-, 6- or
7-membered ring which optionally is substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or said 5-, 6- or 7-membered ring is
substituted by halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; and said 5-, 6- or 7-membered ring
optionally additionally is interrupted by C.sub.1-18alkylene,
C.sub.3-C.sub.30cycloalkylene, C.sub.1-C.sub.8haloalkylene,
C.sub.2-C.sub.12alkenylene, C.sub.4-C.sub.30cycloalkenylene,
phenylene, naphthalene, --O--, --S--, --NR.sub.23--, --(CO)--,
--O(CO)--, --NR.sub.23(CO)--, --S(CO)--, --SO--, --SO.sub.2--, or
--OSO.sub.2--; and optionally one or more benzo radicals are fused
to said 5-, 6- or 7-membered ring; R.sub.5 and R.sub.6
independently of each other are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl;
C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; or
R.sub.5 and R.sub.6 are halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.5 and R.sub.6 together are
--C(R.sub.30).dbd.C(R.sub.31)--C(R.sub.32).dbd.C(R.sub.33)-- or
--(CO)NR.sub.23(CO)--; G is --S--, --O--, --NR.sub.23--, or a group
of formula Z.sub.1, Z.sub.2, Z.sub.3 or Z.sub.4
##STR00013##
R.sub.7 when n is 1, is phenyl, naphthyl, anthracyl, phenanthryl,
or heteroaryl, all of optionally are substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--
or --NR.sub.23(CO)--; or are substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19 form 5-, 6- or 7-membered rings, via the
radicals R.sub.19, R.sub.20, R.sub.21, R.sub.22 and/or R.sub.23,
with further substituents on the phenyl, naphthyl, anthracyl,
phenanthryl, or heteroaryl ring or with one of the carbon atoms of
the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring;
or R.sub.7 is C.sub.1-C.sub.18alkyl; or is C.sub.2-C.sub.18alkyl
which is interrupted by one or more C.sub.3-C.sub.30cycloalkylene,
--O--, --S--, --NR.sub.23--, --(CO)--, --O(CO)--, --S(CO)--,
--NR.sub.23(CO)--, --SO--, --SO.sub.2--, or --OSO.sub.2--;
optionally the radicals C.sub.1-C.sub.18alkyl and
C.sub.2-C.sub.18alkyl are substituted by one or more
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.7 is C.sub.3-C.sub.30cycloalkyl,
optionally interrupted by one or more --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, or --NR.sub.23(CO)--, and optionally
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.7 is hydrogen,
C.sub.1-C.sub.8haloalkyl, --OR.sub.20, --NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --SR.sub.23, C.sub.2-C.sub.12alkenyl,
C.sub.4-C.sub.30cycloalkenyl, camphoryl; and R.sub.7, when n is 2,
is phenylene, naphthylene,
##STR00014##
diphenylene, oxydiphenylene or
##STR00015##
wherein these radicals are optionally substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19, or R.sub.7 is a direct bond,
##STR00016##
wherein all radicals R.sub.7 with the exception of hydrogen and
direct bond optionally additionally are substituted by a group
having a --O--C-bond or a --O--Si-bond which cleaves upon the
.alpha.-tion of an acid; A.sub.4 is a direct bond,
C.sub.1-C.sub.18alkylene, --O--, --S-- or --NR.sub.23--; R.sub.8
and R.sub.9 independently of each other are C.sub.1-C.sub.18alkyl;
or are C.sub.2-C.sub.18alkyl which is interrupted by one or more
C.sub.3-C.sub.30cycloalkylene, --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, --S(CO)--, --NR.sub.23(CO)--, --SO--,
--SO.sub.2--, --OSO.sub.2-- or --Ar.sub.2--; optionally the
radicals C.sub.1-C.sub.18alkyl and C.sub.2-C.sub.18alkyl are
substituted by one or more C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.8 and R.sub.9 are
C.sub.3-C.sub.30cycloalkyl, optionally interrupted by one or more
--O--, --S--, --NR.sub.23--, --(CO)--, --O(CO)--, or
--NR.sub.23(CO)--, and optionally substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.8 and R.sub.9 are hydrogen,
halogen, C.sub.1-C.sub.8haloalkyl, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.8 and R.sub.9, if appropriate,
together with C.sub.1-C.sub.4alkylene, --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, --NR.sub.23(CO)-- form a 5-, 6-, or 7-membered
ring; or R.sub.7 and R.sub.8, if appropriate, together with
C.sub.1-C.sub.3alkylene, --O--, --S--, --NR.sub.23--, --(CO)--,
--O(CO)--, --NR.sub.23(CO)-- form a 5-, 6-, or 7-membered ring;
R.sub.10 has one of the meanings given for R.sub.7; R.sub.11 is
C.sub.1-C.sub.18alkyl; or C.sub.2-C.sub.18alkyl which is
interrupted by one or more C.sub.3-C.sub.30cycloalkylene, --O--,
--S--, --NR.sub.23--, --(CO)--, --O(CO)--, --S(CO)--,
--NR.sub.23(CO)--, --SO--, --SO.sub.2--, --OSO.sub.2-- or
--Ar.sub.2--; optionally the radicals C.sub.1-C.sub.18alkyl and
C.sub.2-C.sub.18alkyl are substituted by one or more
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.11 is C.sub.3-C.sub.30cycloalkyl,
optionally interrupted by one or more --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, or --NR.sub.23(CO)--, and optionally
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.11 is hydrogen,
C.sub.1-C.sub.8haloalkyl, --Ar.sub.1, --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22 or --SO.sub.2R.sub.19; or
R.sub.10 and R.sub.11 together form a 5-, 6- or 7-membered ring
which optionally is substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or said 5-, 6- or 7-membered ring is
substituted by halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; and said 5-, 6- or 7-membered ring
optionally additionally is interrupted by C.sub.1-C.sub.12alkylene,
C.sub.3-C.sub.30cycloalkylene, C.sub.1-C.sub.8haloalkylene,
C.sub.2-C.sub.12alkenylene, C.sub.4-C.sub.30cycloalkenylene,
phenylene, naphthalene, --O--, --S--, --NR.sub.23--, --(CO)--,
--O(CO)--, --NR.sub.23(CO)--, --S(CO)--, --SO--, --SO.sub.2--, or
--OSO.sub.2--; and to said 5-, 6- or 7-membered ring optionally are
fused one or more benzo radicals; R.sub.12, R.sub.13, R.sub.14 and
R.sub.15 independently of each other are hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or R.sub.12, R.sub.13, R.sub.14 and R.sub.15
are halogen, --NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; optionally the substituents R.sub.12,
R.sub.13, R.sub.14 and/or R.sub.15 form 5-, 6- or 7-membered rings
or fused rings, via the radicals R.sub.12, R.sub.13, R.sub.14
and/or R.sub.15 with further substituents on the phenyl to which
R.sub.12, R.sub.13, R.sub.14 and R.sub.15 are bonded, or with one
of the carbon atoms of said phenyl ring; wherein all radicals
radicals R.sub.12, R.sub.13, R.sub.14 and/or R.sub.15 with the
exception of hydrogen optionally additionally are substituted by a
group having a --O--C-bond or a --O--Si-bond which cleaves upon the
action of an acid; R.sub.16, R.sub.17 and R.sub.10 independently of
each other are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl;
C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; or
R.sub.16, R.sub.17 and R.sub.18 are halogen, --NO.sub.2, --CN,
--Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents R.sub.16,
R.sub.17, and/or R.sub.18 form 5-, 6- or 7-membered rings or fused
rings, via the radicals R.sub.16, R.sub.17, and/or R.sub.18 with
further substituents on the phenyl ring to which R.sub.16, R.sub.17
and R.sub.18 are bonded or with one of the carbon atoms of said
phenyl ring; wherein all radicals radicals R.sub.16, R.sub.17,
and/or R.sub.18 with the exception of hydrogen optionally
additionally are substituted by a group having a --O--C-bond or a
--O--Si-bond which cleaves upon the action of an acid;
[0008] R.sub.19 is phenyl, naphthyl, C.sub.3-C.sub.30cycloalkyl,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.2-C.sub.12alkenyl, C.sub.4-C.sub.30cycloalkenyl; or is
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--; or
is C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; all
of which optionally are substituted by one or more Ar.sub.1, OH,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.19 is hydrogen;
R.sub.20 is phenyl, naphthyl, C.sub.3-C.sub.30cycloalkyl,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.2-C.sub.12alkenyl, C.sub.4-C.sub.30cycloalkenyl; or is
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--; or
is C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)-- or --NR.sub.23(CO)--; or is
C.sub.2-C.sub.18alkanoyl, or is benzoyl, or is
C.sub.1-C.sub.18alkylsulfonyl, all of which optionally are
substituted by one or more Ar.sub.1, OH, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl,
phenylthio, phenylthiocarbonyl, --NR.sub.21R.sub.22,
C.sub.1-C.sub.12alkylthio, C.sub.2-C.sub.12alkoxycarbonyl,
C.sub.2-C.sub.8haloalkanoyl, halobenzoyl,
C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.20 is hydrogen, phenylsulfonyl,
(4-methylphenyl)sulfonyl, naphthylsulfonyl, anthracylsulfonyl or
phenanthrylsulfonyl; R.sub.21, R.sub.22 and R.sub.23 independently
of each other are phenyl, naphthyl, C.sub.3-C.sub.30cycloalkyl,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.2-C.sub.12alkenyl, C.sub.4-C.sub.30cycloalkenyl; or are
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--; or
are C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; or
are C.sub.2-C.sub.18alkanoyl, benzoyl or
C.sub.1-C.sub.18alkylsulfonyl, all of which optionally are
substituted by one or more Ar.sub.1, OH, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl,
phenylthio, phenylthiocarbonyl, --NR.sub.21R.sub.22,
C.sub.1-C.sub.12alkylthio, C.sub.2-C.sub.12alkoxycarbonyl,
C.sub.2-C.sub.8haloalkanoyl, halobenzoyl,
C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.21, R.sub.22 and R.sub.23
independently of each other are hydrogen, phenylsulfonyl,
(4-methylphenyl)sulfonyl, naphthylsulfonyl, anthracylsulfonyl or
phenanthrylsulfonyl; or R.sub.2, and R.sub.22, together with the
nitrogen atom to which they are attached, form a 5-, 6- or
7-membered ring which optionally is interrupted by --O-- or by
--NR.sub.23--; R.sub.24 is phenyl, naphthyl,
C.sub.3-C.sub.30cycloalkyl, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.4-C.sub.30cycloalkenyl; or is
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--, or
is C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; all
of which are unsubstituted or substituted by one or more Ar.sub.1,
OH, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8-haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.24 is hydrogen; or R.sub.23 and
R.sub.24 together with the N-atom to which they are attached form a
5-, 6- or 7-membered ring which optionally is interrupted by --CO--
or --O-- and which additionally optionally is fused with one or
more benzo rings; R.sub.25, R.sub.26 and R.sub.27 independently of
each other are hydrogen; or are phenyl or naphthyl, both of which
optionally are substituted by one or more Ar.sub.1, OH,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.25, R.sub.26 and R.sub.27 are
C.sub.3-C.sub.18alkenyl or C.sub.3-C.sub.18alkynyl; or R.sub.25,
R.sub.26 and R.sub.27 are C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--,
and wherein the radicals C.sub.1-C.sub.18alkyl and
C.sub.2-C.sub.18alkyl are optionally substituted by one or more
Ar.sub.1, OH, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.25 and R.sub.26, if appropriate
together with C.sub.1-C.sub.2alkylene, --O--, --S--, or --CO--,
form a fused ring; or R.sub.25, R.sub.26 and R.sub.27, if
appropriate together with C.sub.1-C.sub.2alkylene, --O--, --S--, or
--CO--, form a 5-, 6-, or 7-membered ring; or R.sub.25, R.sub.26
and R.sub.27 together with the N.sup.+-atom to which they are
bonded forma group
##STR00017##
R.sub.28 and R.sub.29 independently of each other are phenyl which
optionally is substituted by one or more Ar.sub.1, OH,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.28 and R.sub.29 independently of
each other are C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkyl which
is interrupted by one or more --O--, and wherein the radicals
C.sub.1-C.sub.18alkyl and C.sub.2-C.sub.18alkyl are optionally
substituted by one or more Ar.sub.1, OH, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl,
phenylthio, phenylthiocarbonyl, --NR.sub.21R.sub.22,
C.sub.1-C.sub.12alkylthio, C.sub.2-C.sub.12alkoxycarbonyl,
C.sub.2-C.sub.8haloalkanoyl, halobenzoyl,
C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.28 and R.sub.29, if appropriate
together with C.sub.1-C.sub.2alkylene, --O--, --S--, or --CO--,
form a fused ring; or R.sub.28 and R.sub.29, if appropriate
together with C.sub.1-C.sub.2alkylene, --O--, --S--, or --CO--,
form a 5-, 6- or 7-membered ring; R.sub.30, R.sub.31, R.sub.32 and
R.sub.33 are independently of each other hydrogen, halogen,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkoxy,
C.sub.1-C.sub.8haloalkyl, CN, NO.sub.2, C.sub.2-C.sub.18alkanoyl,
benzoyl, phenyl, --S-phenyl, OR.sub.20, SR.sub.23,
NR.sub.21R.sub.22, C.sub.2-C.sub.6alkoxycarbonyl, phenoxycarbonyl,
S(O).sub.pC.sub.1-C.sub.18alkyl, unsubstituted or
C.sub.1-C.sub.18alkyl-substituted S(O)P--C.sub.6-C.sub.12aryl,
SO.sub.2O--C.sub.1-C.sub.18alkyl, SO.sub.2O--C.sub.6-C.sub.10aryl
or NHCONH.sub.2; R.sub.34 and R.sub.35 independently of each other
have one of the meanings given for R.sub.5; or R.sub.34 and
R.sub.35 together are --CO--NR.sub.23CO--; or R.sub.34 and R.sub.35
together are
--C(R.sub.30).dbd.C(R.sub.31)--C(R.sub.32).dbd.C(R.sub.33)--;
Ar.sub.1 is phenyl, naphthyl, anthracyl, phenanthryl, or
heteroaryl, all of which optionally are substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or are substituted by halogen, --NO.sub.2,
--CN, phenyl, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19 form 5-, 6- or 7-membered rings, via the
radicals R.sub.19, R.sub.20, R.sub.21, R.sub.22 and/or R.sub.23,
with further substituents on the phenyl, naphthyl, anthracyl,
phenanthryl, or heteroaryl ring or with one of the carbon atoms of
the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring;
Ar.sub.2 is phenylene, naphthylene,
##STR00018##
diphenylene, oxydiphenylene or
##STR00019##
wherein these radicals optionally are substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19, optionally the substituents
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19 form 5-, 6- or 7-membered rings, via the
radicals R.sub.19, R.sub.20, R.sub.21, R.sub.22 and/or R.sub.23,
with further substituents on these radicals or with one of the
carbon atoms of these radicals;
M.sup.+ is
##STR00020##
[0009] R.sub.43--I.sup.+--R.sub.44, Li.sup.+, Na.sup.+, K.sup.+,
Cs.sup.+, 1/2Mg.sup.2+, 1/2Ca.sup.2+ or 1/2Ba.sup.2+; L.sup.- is
F.sup.-, Cl.sup.-, Br.sup.-, I.sup.-, HSO.sub.4.sup.-,
1/2SO.sub.4.sup.2-, NO.sub.3.sup.-,
##STR00021##
ClO.sub.4.sup.-, BF.sub.4.sup.31, PF.sub.6.sup.-, AsF.sub.6.sup.-,
SbF.sub.6.sup.-, (R.sub.50SO.sub.2).sub.3C.sup.- or
(R.sub.50SO.sub.2).sub.2N.sup.-; R.sub.36, R.sub.37, R.sub.38 and
R.sub.39 have one of the meanings given for R.sub.25, R.sub.26 and
R.sub.27; R.sub.40, R.sub.41 and R.sub.42 have one of the meanings
given for R.sub.28 and R.sub.29; R.sub.43 and R.sub.44
independently of each other are phenyl, which optionally is
substituted by one or more Ar.sub.1, OH, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl,
phenylthio, phenylthiocarbonyl, --NR.sub.21R.sub.22,
C.sub.1-C.sub.12alkylthio, C.sub.2-C.sub.12alkoxycarbonyl,
C.sub.2-C.sub.8haloalkanoyl, halobenzoyl,
C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.43 and R.sub.44, if appropriate
together with C.sub.1-C.sub.2alkylene, --O--, --S--, or --CO--,
form a fused ring; R.sub.45 is C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, camphoryl, phenyl-C.sub.1-C.sub.3alkyl,
C.sub.3-C.sub.30cycloalkyl, C.sub.4-C.sub.30cycloalkenyl, phenyl,
naphthyl, anthracyl or phenanthryl; all of which optionally are
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; R.sub.46 and R.sub.47 independently of one
another have one of the meanings given for R.sub.5; or R.sub.46 and
R.sub.47 together are --CO--NR.sub.23--CO-- or
--C(R.sub.30).dbd.C(R.sub.31)--C(R.sub.32).dbd.C(R.sub.33)--;
R.sub.48 and R.sub.49 independently of one another have on of the
meanings given for R.sub.5; or R.sub.48 and R.sub.49 together are
--CO--NR.sub.23--CO-- or
--C(R.sub.30).dbd.C(R.sub.31)--C(R.sub.32).dbd.C(R.sub.33)--;
R.sub.50 is C.sub.1-C.sub.8-perfluoroalkyl;
Q.sub.1 is --CR.sub.35-- or --N--; and
Q.sub.2 is --CH.sub.2--, --S--, --O-- or --NR.sub.23--.
[0010] The compounds of the formulae Ia, Ib, IIa, IIb, IIIa, IIIb,
IVa, IVb, Va, Vb and VIa are characterized in that they are
composed of photoactive moieties with linear
C.sub.2-C.sub.6alkylsulfonate bearing a functional group or with
vinylsulfonate.
[0011] C.sub.1-C.sub.18alkyl is linear or branched and is, for
example, C.sub.1-C.sub.16--, C.sub.1-C.sub.12--, C.sub.1-C.sub.8--,
C.sub.1-C.sub.6-- or C.sub.1-C.sub.4-alkyl. Examples are methyl,
ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,
pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl,
nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl,
heptadecyl and octadecyl, preferably C.sub.1-C.sub.4alkyl, such as
methyl, isopropyl or butyl.
[0012] C.sub.2-C.sub.18alkyl, which is interrupted once or several
times by --O--, is interrupted, for example, from one to five
times, for example from one to three times or once or twice, by
non-successive --O--. Accordingly, resulting structural units are
for example: --O(CH.sub.2).sub.2OH, --O(CH.sub.2).sub.2OCH.sub.3,
--O(CH.sub.2CH.sub.2O).sub.2CH.sub.2CH.sub.3,
--CH.sub.2--O--CH.sub.3, --CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.3,
--[CH.sub.2CH.sub.2O].sub.y--CH.sub.3, wherein y=1-5,
--(CH.sub.2CH.sub.2O).sub.5CH.sub.2CH.sub.3,
--CH.sub.2--CH(CH.sub.3)--O--CH.sub.2--CH.sub.2CH.sub.3 or
--CH.sub.2--CH(CH.sub.3)--O--CH.sub.2--CH.sub.3.
[0013] C.sub.3-C.sub.30cycloalkyl is a mono- or polycyclic
aliphatic ring, for example a mono-, bi- or tricyclic aliphatic
ring, e.g. C.sub.3-C.sub.20--, C.sub.3-C.sub.18--,
C.sub.3-C.sub.12--, C.sub.3-C.sub.10cycloalkyl. Examples of
monocyclic rings are cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, or cycloheptyl, especially cyclopentyl and cyclohexyl.
Examples of polycyclic rings are perhydroanthracyl,
perhydrophenyathryl, perhydronaphthyl, perhydrofluorenyl,
perhydrochrysenyl, perhydropicenyl, adamantyl,
bicyclo-[1.1.1]pentyl, bicyclo[4.2.2]decyl, bicyclo[2.2.2]octyl,
bicyclo[3.3.2]decyl, bicyclo[4.3.2]undecyl, bicyclo[4.3.3]dodecyl,
bicyclo[3.3.3]undecyl, bicyclo[4.3.1]decyl, bicyclo[4.2.1]nonyl,
bicyclo[3.3.1]nonyl, bicyclo[3.2.1]octyl and the like. Also
"spiro"-cycloalkyl compounds are covered by the definition
C.sub.3-C.sub.30cycloalkyl in the present context, e.g.
spiro[5.2]octyl, spiro[5.4]decyl, spiro[5.5]undecyl. More examples
of polycyclic cycloalkyl groups, which are subject of the
respective definition in the compounds of the present invention are
listed in EP 878738, page 11 and 12, wherein to the formulae
(I)-(46) a bond to achieve the "yl" has to be added. The person
skilled in the art is aware of this fact.
[0014] In general, the cycloaliphatic rings may form repeating
structural units.
[0015] C.sub.3-C.sub.30cycloalkyl which is interrupted by one or
more --O--, --S--, --NR.sub.23--, --O(CO)--, --SCO--,
--NR.sub.23CO--, is a mono- or polycyclic aliphatic ring which is
interrupted by one or more --O--, --S--, --NR.sub.6--, --O(CO)--,
--SCO--, --NR.sub.6CO--, for example
##STR00022##
[0016] C.sub.2-C.sub.12alkenyl radicals may be mono- or
polyunsaturated, linear or branched and are for example
C.sub.2-C.sub.8--, C.sub.2-C.sub.6-- or C.sub.2-C.sub.4alkenyl.
Examples are allyl, methallyl, vinyl, 1,1-dimethylallyl, 1-butenyl,
3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl or 7-octenyl,
especially allyl or vinyl.
[0017] C.sub.4-C.sub.30cycloalkenyl is a mono- or polycyclic and
polyunsaturated ring, for example a mono-, bi- or tricyclic
polyunsaturated ring, e.g. C.sub.4-C.sub.20--, C.sub.4-C.sub.18--,
C.sub.4-C.sub.12--, C.sub.4-C.sub.10cycloalkenyl. Examples of
cycloalkenyl are cyclobutenyl, cyclopentenyl, cyclohexenyl, or
cycloheptenyl, especially cyclopentenyl and cyclohexenyl.
[0018] C.sub.1-C.sub.18alkylene is linear or branched and is, for
example, C.sub.1-C.sub.8--, C.sub.1-C.sub.6-- or
C.sub.1-C.sub.4-alkylene. Examples are methylene, ethylene,
propylene, butylene, pentylene, hexylene, heptylene,
.alpha.-tylene, nonylene, decylene, undecylene and dodecylene.
Preferred is C.sub.1-C.sub.8alkylene, especially
C.sub.1-C.sub.6alkylene, preferably C.sub.1-C.sub.4alkylene, such
as ethylene or butylene.
[0019] C.sub.3-C.sub.30cycloalkylene is a biradical of mono- or
polycyclic aliphatic ring, for example a mono-, bi- or tricyclic
aliphatic ring, e.g. C.sub.3-C.sub.20--, C.sub.3-C.sub.18--,
C.sub.3-C.sub.12--, C.sub.3-C.sub.10cycloalkylene. Examples of
monocyclic rings are cyclopropylene, cyclobutylene, cyclopentylene,
cyclohexylene or cycloheptylene, especially cyclohexylene. Examples
of polycyclic rings are perhydroanthracylene,
perhydrophenyathrylene, perhydronaphthylene, perhydrofluorenylene,
perhydrochrysenylene, perhydropicenylene, adamantylene,
bicyclo[1.1.1]pentylene, bicyclo[4.2.2]decylene,
bicyclo[2.2.2]octylene, bicyclo[3.3.2]decylene,
bicyclo[4.3.2]undecylene, bicyclo[4.3.3]dodecylene,
bicyclo[3.3.3]undecylene, bicyclo[4.3.1]decylene,
bicyclo[4.2.1]nonylene, bicyclo[3.3.1]-nonylene,
bicyclo[3.2.1]octylene and the like. Also "spiro"-cycloalkyl
compounds are covered by the definition
C.sub.3-C.sub.30cycloalkylene in the present context, e.g.
spiro[5.2]octylene, spiro-[5.4]decylene, spiro[5.5]undecylene.
[0020] In general, the cycloaliphatic rings may form repeating
structural units.
[0021] C.sub.1-C.sub.8Haloalkylene is C.sub.1-C.sub.8-alkylene
mono- or poly-substituted by halogen, C.sub.1-C.sub.8-alkylene
being, for example, as defined above. There are, for example, from
one to three or one or two halogen substituents at the alkylene
radical. Examples are chloromethylene, dichloromethylene,
difluoromethylene or 2-bromopropylene, especially difluoromethylene
or dichloromethylene.
[0022] C.sub.2-C.sub.12alkenylene radicals may be mono- or
polyunsaturated, linear or branched and are for example
C.sub.2-C.sub.8--, C.sub.2-C.sub.6-- or C.sub.2-C.sub.4alkenylene.
Examples are vinylene, propenylene, but-1-enylene, but-2-enylene,
penta-1,3-dienylene, especially vinylene.
[0023] C.sub.4-C.sub.8cycloalkenylene, may have one or more double
bonds and is for example C.sub.4-C.sub.6-cycloalkenylene or
C.sub.6-C.sub.8-cycloalkenylene. Examples are cyclobutenylene,
cyclopentenylene, cyclohexenylene or cyclooctenylene, especially
cyclopentenylene and cyclohexenylene, preferably
cyclohexenylene.
[0024] Substituted phenyl carries from one to five, for example
one, two or three, especially one or two, substituents on the
phenyl ring. The substitution is preferably in the 4-, 3,4-, 3,5-
or 3,4,5-position of the phenyl ring.
[0025] When the radicals naphthyl, phenanthryl and anthracyl are
substituted by one or more radicals, they are, for example, mono-
to penta-substituted, for example mono-, di- or trisubstituted,
especially mono- or di-substituted.
[0026] Camphoryl, 10-camphoryl, are camphor-10-yl, namely
##STR00023##
[0027] C.sub.2-C.sub.18alkanoyl is e.g. C.sub.2-C.sub.12,
C.sub.2-C.sub.8-, C.sub.2-C.sub.6-- or C.sub.2-C.sub.4alkanoyl,
wherein the alkyl moiety is linear or branched. Examples are
acetyl, propionyl, butanoyl or hexanoyl, especially acetyl.
[0028] C.sub.1-C.sub.18alkoxy is e.g. C.sub.1-C.sub.12--,
C.sub.1-C.sub.8-, C.sub.1-C.sub.6-, C.sub.1-C.sub.4alkoxy, and is
linear or branched. Examples are methoxy, ethoxy, propoxy,
n-butoxy, t-butoxy, octyloxy and dodecyloxy.
[0029] In C.sub.1-C.sub.12alkylthio the alkyl moiety is for example
linear or branched. Examples are methylthio, ethylthio, propylthio
or butylhtio.
[0030] C.sub.2-C.sub.12alkoxycarbonyl is
(C.sub.1-C.sub.11alkyl)-O--C(O)--, wherein C.sub.1-C.sub.11alkyl is
linear or branched and is as defined above up to the appropriate
number of carbon atoms. Examples are C.sub.2-C.sub.10-,
C.sub.2-C.sub.8-, C.sub.2-C.sub.6-- or
C.sub.2-C.sub.4alkoxycarbonyl, such as methoxycarbonyl,
ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl or
pentoxycarbonyl.
[0031] C.sub.1-C.sub.8haloalkyl are for example C.sub.1-C.sub.8-,
C.sub.1-C.sub.6-- or C.sub.1-C.sub.4-alkyl mono- or
poly-substituted by halogen, the alkyl moieties being, for example,
as defined above. There are, for example, from one to three or one
or two halogen substituents at the alkyl radical. Examples are
chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl,
especially trifluoromethyl or trichloromethyl. Preferred is
C.sub.1-C.sub.10fluoroalkyl.
[0032] C.sub.1-C.sub.8 perfluoroalkyl is linear or branched
per-fluorinated C.sub.1-C.sub.8alkyl, and is e.g. C.sub.1-C.sub.6-,
C.sub.1-C.sub.4--, C.sub.4-C.sub.8-perfluoroalkyl. Examples are
trifluoromethyl, pentafluoroethyl, heptafluoropropyl,
heptafluoroisopropyl, octafluoro-n-butyl, octafluoro-sec-butyl,
octafluoro-isobutyl, octafluoro-tert-butyl, decafluoropentyl,
dodecafluorohexyl, tridecafluoroheptyl or heptadecafluorooctyl.
[0033] C.sub.2-C.sub.8haloalkanoyl is
(C.sub.1-C.sub.5haloalkyl)-C(O)--, wherein C.sub.1-C.sub.5haloalkyl
is as defined above up to the appropriate number of carbon atoms.
Examples are chloroacetyl, trichloroacetyl, trifluoroacetyl,
pentafluoropropionyl, perfluorooctanoyl, or 2-bromopropionyl,
especially trifluoroacetyl or trichloroacetyl.
[0034] Halobenzoyl is benzoyl which is mono- or poly-substituted by
halogen and/or C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4-haloalkyl
being as defined above. Examples are pentafluorobenzoyl,
trichlorobenzoyl, trifluoromethylbenzoyl, especially
pentafluorobenzoyl.
[0035] Halogen is fluorine, chlorine, bromine or iodine, especially
chlorine or fluorine, preferably fluorine.
[0036] Phenyl-C.sub.1-C.sub.3alkyl is, for example, benzyl,
2-phenylethyl, 3-phenylpropyl, .alpha.-methylbenzyl or
.alpha.,.alpha.-dimethylbenzyl, especially benzyl.
[0037] Oxydiphenylene is
##STR00024##
[0038] If R.sub.21 and R.sub.22 together with the nitrogen atom to
which they are bonded form a 5-, 6- or 7-membered ring that
optionally is interrupted by --O-- or by --NR.sub.23--, for example
the following structures are obtained
##STR00025##
[0039] If R.sub.23 and R.sub.24 together with the nitrogen atom to
which they are bonded form a 5-, 6- or 7-membered ring that
optionally is interrupted by --CO-- ant to which optionally benzo
rings are fused, for example the following structures are
obtained
##STR00026##
[0040] The definitions C.sub.1-C.sub.18alkylsulfonyl,
phenyl-C.sub.1-C.sub.3alkylsulfonyl, camphorylsulfonyl,
C.sub.1-C.sub.10haloalkylsulfonyl refer to the corresponding
radicals C.sub.1-C.sub.18alkyl, phenyl-C.sub.1-C.sub.3alkyl,
camphoryl and C.sub.1-C.sub.10haloalkyl, as described in detail
above, being linked to a sulfonyl group (--SO.sub.2--).
Accordingly, also phenylsulfonyl, naphthylsulfonyl,
anthracylsulfonyl and phenanthrylsulfonyl refer to the
corresponding radicals linked to a sulfonyl group. R.sub.6 is for
example C.sub.2-C.sub.18-, C.sub.4-C.sub.12-, C.sub.6-C.sub.18-,
C.sub.4-C.sub.10-alkylsulfonyl.
[0041] C.sub.6-C.sub.12aryl is for example phenyl, biphenylyl or
naphthyl and C.sub.6-C.sub.10aryl is phenyl or naphthyl. If
R.sub.10 and R.sub.11 together form a 5-, 6- or 7-membered ring
that is unsubstituted or substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or is substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, and said ring may additionally be interrupted
by C.sub.1-12alkylene, C.sub.3-C.sub.30cycloalkylene,
C.sub.1-C.sub.8haloalkylene, C.sub.2-C.sub.12alkenylene,
C.sub.4-C.sub.30cycloalkenylene, phenylene, naphthalene, --O--,
--S--, --NR.sub.23--, --(CO)--, --O(CO)--, --NR.sub.23(CO)--,
--S(CO)--, --SO--, --SO.sub.2--, or --OSO.sub.2--, and to which
ring one or more benzo radicals may be fused, for example the
following structures are obtained
##STR00027##
[0042] Groups having a --O--C-bond or a --O--Si-bond which cleaves
upon the action of an acid, and being substituents of the radicals
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.7, R.sub.10, R.sub.12,
R.sub.13, R.sub.14, R.sub.15, R.sub.16, R.sub.17, R.sub.18 and
R.sub.19 are acid cleavable groups which increase the solubility of
the compounds of formula Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb,
Va, Vb or VIa in the alkaline developer after reaction with an
acid. This effect is for example described in U.S. Pat. No.
4,883,740.
Examples of groups suitable as such substitutents are for example
known orthoesters, trityl and benzyl groups, tert.-butyl esters of
carboxylic acids, tert.-butyl carbonates of phenols or silyl ethers
of phenols, e.g. --OSi(CH.sub.3).sub.3,
##STR00028##
wherein R'.sub.1 and R'.sub.2 independently of one another are
hydrogen, C.sub.1-C.sub.5alkyl, C.sub.3-C.sub.8-cycloalkyl,
phenyl-C.sub.1-C.sub.3-alkyl, or R'.sub.1 and R'.sub.2 together are
C.sub.2-C.sub.5alkylene, and R'.sub.3 is unsubstituted or
halogen-substituted C.sub.1-C.sub.5alkyl, unsubstituted or
halogen-substituted C.sub.3-C.sub.8cycloalkyl, or
phenyl-C.sub.1-C.sub.3-alkyl, or, if R'.sub.1 and R'.sub.2 together
are no C.sub.2-C.sub.5alkylene, R.sub.13 and R'.sub.2 together may
be C.sub.2-C.sub.5alkylene, which may be interrupted by an --O-atom
or an --S-atom.
[0043] The terms "and/or" or "or/and" in the claims and throughout
the specification are meant to express that not only one of the
defined alternatives (substituents) may be present, but also
several of the defined alternatives (substituents) together, namely
mixtures of different alternatives (substituents).
[0044] The term "optionally substituted" means unsubstituted or
substituted.
[0045] The term "at least" is meant to define one or more than one,
for example one or two or three, preferably one or two.
[0046] The invention also pertains to novel compounds of the
formulae Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa
##STR00029## ##STR00030##
n is 1 or 2; m is 0 or 1; X.sub.0 is --[CH.sub.2].sub.h--X or
--CH.dbd.CH.sub.2; h is 2, 3, 4, 5 or 6; R.sub.1 when n is 1, is
phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl, all of
which are optionally substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or are substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19 form 5-, 6- or 7-membered rings, via the
radicals R.sub.19, R.sub.20, R.sub.21, R.sub.22 and/or R.sub.23,
with further substituents on the phenyl, naphthyl, anthracyl,
phenanthryl, or heteroaryl ring or with one of the carbon atoms of
the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring;
or R.sub.1 is hydrogen, with the proviso that R.sub.2 is not
simultaneously hydrogen; or R.sub.1 is C.sub.1-C.sub.18alkyl; or is
C.sub.2-C.sub.18alkyl which is interrupted by one or more
C.sub.3-C.sub.30cycloalkylene, --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, --S(CO)--, --NR.sub.23(CO)--, --SO--,
--SO.sub.2--, or --OSO.sub.2--; optionally the radicals
C.sub.1-C.sub.18alkyl and C.sub.2-C.sub.18alkyl are substituted by
one or more C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl,
halogen, --NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.1 is
C.sub.3-C.sub.30cycloalkyl, optionally interrupted by one or more
--O--, --S--, --NR.sub.23--, --(CO)--, --O(CO)--, or
--NR.sub.23(CO)--, and which is unsubstituted or substituted by one
or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.1 is C.sub.1-C.sub.8haloalkyl,
C.sub.2-C.sub.12alkenyl, C.sub.4-C.sub.30cycloalkenyl, camphoryl;
or if m is 0, R.sub.1 additionally is CN,
C.sub.2-C.sub.6alkoxycarbonyl or phenoxycarbonyl, wherein
C.sub.2-C.sub.6alkoxycarbonyl and phenoxycarbonyl optionally are
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl;
C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; or
are substituted by halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; R.sub.1, when n is 2, is phenylene,
naphthylene,
##STR00031##
diphenylene, oxydiphenylene or
##STR00032##
wherein these radicals are unsubstituted or substituted by one or
more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19, or R.sub.1 is a direct bond
##STR00033##
wherein all radicals R.sub.1 with the exception of hydrogen and
direct bond can additionally be substituted by a group having a
--O--C-bond or a --O--Si-bond which cleaves upon the action of an
acid; A.sub.1 is a direct bond, C.sub.1-C.sub.18alkylene, --O--,
--S--, --NR.sub.23--, --O(CO)--, --S(CO)--, --NR.sub.23(CO)--,
--SO--, --SO.sub.2-- or --OSO.sub.2--; A.sub.2 is a direct bond,
C.sub.1-C.sub.18alkylene; or is C.sub.2-C.sub.18alkylene which is
interrupted by one or more C.sub.3-C.sub.30cycloalkylene, --O--,
--S--, --NR.sub.23--, --(CO)--, --O(CO)--, --S(CO)--,
--NR.sub.23(CO)--, --SO--, --SO.sub.2--, --OSO.sub.2-- or
--Ar.sub.2--; optionally the radicals C.sub.1-C.sub.18alkylene and
C.sub.2-C.sub.18alkylene are substituted by one or more
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or A.sub.2 is C.sub.3-C.sub.30cycloalkylene,
optionally interrupted by one or more --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, or --NR.sub.23(CO)--, and which is
unsubstituted or substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or A.sub.2 is phenylene, naphthylene, wherein
these radicals optionally are substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; R.sub.2 has one of the meanings of
R.sub.1 or is C.sub.2-C.sub.18alkanoyl; benzoyl that is
unsubstituted or substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.2 is NO.sub.2; or R.sub.2 is
S(O).sub.pC.sub.1-C.sub.18alkyl, S(O).sub.p--C.sub.6-C.sub.12aryl,
SO.sub.2O--C.sub.1-C.sub.18alkyl, SO.sub.2O--C.sub.6-C.sub.10aryl,
diphenyl-phosphinoyl, all of which optionally are substituted by
one or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or are substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.1 and R.sub.2 together form a 5-, 6-
or 7-membered ring which is unsubstituted or substituted by one or
more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or is substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; and said 5-, 6- or 7-membered ring may
additionally be interrupted by C.sub.1-18alkylene,
C.sub.3-C.sub.30cycloalkylene, C.sub.1-C.sub.8haloalkylene,
C.sub.2-C.sub.12alkenylene, C.sub.4-C.sub.30cycloalkenylene,
phenylene, naphthalene, --O--, --S--, --NR.sub.23--, --(CO)--,
--O(CO)--, --NR.sub.23(CO)--, --S(CO)--, --SO--, --SO.sub.2--, or
--OSO.sub.2--, and to said 5-, 6- or 7-membered ring optionally are
fused one or more benzo radicals; p is 1 or 2; X is
--O(CO)R.sub.24, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.24, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19,
--OSO.sub.2R.sub.19, or the groups
##STR00034##
X' is -X.sub.1-A.sub.3-X.sub.2-;
[0047] X.sub.1 and X.sub.2 independently of each other are
--O(CO)--, --O(CO)O--, --O(CO)NR.sub.23--, --NR.sub.23(CO)--,
--NR.sub.23(CO)O--, --O--, --NR.sub.23--, --S--, --SO--,
--SO.sub.2--, --OSO.sub.2--,
##STR00035##
or X.sub.1 and X.sub.2 are a direct bond, with the proviso that
X.sub.1 and X.sub.2 are not both simultaneously a direct bond;
A.sub.3 is phenylene, naphthylene,
##STR00036##
diphenylene, oxydiphenylene or
##STR00037##
wherein these radicals are unsubstituted or substituted by one or
more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19,
[0048] or As is a direct bond,
##STR00038##
R.sub.3 has one of the meanings given for R.sub.1; or R.sub.3 is
C.sub.2-C.sub.18alkanoyl; benzoyl which optionally is substituted
by one or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.3 is NO.sub.2; or R.sub.3 is
S(O)PC.sub.1-C.sub.18alkyl, S(O).sub.p--C.sub.6-C.sub.12aryl,
SO.sub.2O--C.sub.1-C.sub.18alkyl, SO.sub.2O--C.sub.6-C.sub.10aryl,
diphenyl-phosphinoyl, all of which optionally are substituted by
one or more C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or is substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; R.sub.4 has one of the meaning given for
R.sub.2, or R.sub.3 and R.sub.4 together form a 5-, 6- or
7-membered ring which optionally is substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or said 5-, 6- or 7-membered ring is
substituted by halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; and said 5-, 6- or 7-membered ring
optionally additionally is interrupted by C.sub.1-18alkylene,
C.sub.3-C.sub.30cycloalkylene, C.sub.1-C.sub.8haloalkylene,
C.sub.2-C.sub.12alkenylene, C.sub.4-C.sub.30cycloalkenylene,
phenylene, naphthalene, --O--, --S--, --NR.sub.23--, --(CO)--,
--O(CO)--, --NR.sub.23(CO)--, --S(CO)--, --SO--, --SO.sub.2--, or
--OSO.sub.2--; and optionally one or more benzo radicals are fused
to said 5-, 6- or 7-membered ring; R.sub.5 and R.sub.6
independently of each other are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl;
C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; or
R.sub.5 and R.sub.6 are halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.5 and R.sub.6 together are
--C(R.sub.30).dbd.C(R.sub.31)--C(R.sub.32).dbd.C(R.sub.33)-- or
--(CO)NR.sub.23(CO)--; G is --S--, --O--, --NR.sub.23--, or a group
of formula Z.sub.1, Z.sub.2, Z.sub.3 or Z
##STR00039##
R.sub.7 when n is 1, is phenyl, naphthyl, anthracyl, phenanthryl,
or heteroaryl, all of optionally are substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--
or --NR.sub.23(CO)--; or are substituted by halogen, --NO.sub.2,
--CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19 form 5-, 6- or 7-membered rings, via the
radicals R.sub.19, R.sub.20, R.sub.21R.sub.22 and/or R.sub.23, with
further substituents on the phenyl, naphthyl, anthracyl,
phenanthryl, or heteroaryl ring or with one of the carbon atoms of
the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring;
or R.sub.7 is C.sub.1-C.sub.18alkyl; or is C.sub.2-C.sub.18alkyl
which is interrupted by one or more C.sub.3-C.sub.30cycloalkylene,
--O--, --S--, --NR.sub.23--, --(CO)--, --O(CO)--, --S(CO)--,
--NR.sub.23(CO)--, --SO--, --SO.sub.2--, or --OSO.sub.2--;
optionally the radicals C.sub.1-C.sub.18alkyl and
C.sub.2-C.sub.18alkyl are substituted by one or more
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.7 is C.sub.3-C.sub.30cycloalkyl,
optionally interrupted by one or more --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, or --NR.sub.23(CO)--, and optionally
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.11; or R.sub.7 is hydrogen,
C.sub.1-C.sub.8haloalkyl, --OR.sub.20, --NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --SR.sub.23, C.sub.2-C.sub.12alkenyl,
C.sub.4-C.sub.30cycloalkenyl, camphoryl; and R.sub.7, when n is 2,
is phenylene, naphthylene,
##STR00040##
diphenylene, oxydiphenylene or
##STR00041##
wherein these radicals are optionally substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19, or R.sub.7 is a direct bond,
##STR00042##
wherein all radicals R.sub.7 with the exception of hydrogen and
direct bond optionally additionally are substituted by a group
having a --O--C-bond or a --O--Si-bond which cleaves upon the
action of an acid; A.sub.4 is a direct bond,
C.sub.1-C.sub.18alkylene, --O--, --S-- or --NR.sub.23--; R.sub.8
and R.sub.9 independently of each other are C.sub.1-C.sub.18alkyl;
or are C.sub.2-C.sub.18alkyl which is interrupted by one or more
C.sub.3-C.sub.30cycloalkylene, --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, --S(CO)--, --NR.sub.23(CO)--, --SO--,
--SO.sub.2--, --OSO.sub.2-- or --Ar.sub.2--; optionally the
radicals C.sub.1-C.sub.18alkyl and C.sub.2-C.sub.18alkyl are
substituted by one or more C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.8 and R.sub.9 are
C.sub.3-C.sub.30cycloalkyl, optionally interrupted by one or more
--O--, --S--, --NR.sub.23--, --(CO)--, --O(CO)--, or
--NR.sub.23(CO)--, and optionally substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.8 and R.sub.9 are hydrogen,
halogen, C.sub.1-C.sub.8haloalkyl, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; or R.sub.8 and R.sub.9, if appropriate,
together with C.sub.1-C.sub.4alkylene, --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, --NR.sub.23(CO)-- form a 5-, 6-, or 7-membered
ring; or R.sub.7 and R.sub.8, if appropriate, together with
C.sub.1-C.sub.3alkylene, --O--, --S--, --NR.sub.23--, --(CO)--,
--O(CO)--, --NR.sub.23(CO)-- form a 5-, 6-, or 7-membered ring;
R.sub.10 has one of the meanings given for R.sub.7; R.sub.11 is
C.sub.1-C.sub.18alkyl; or C.sub.2-C.sub.18alkyl which is
interrupted by one or more C.sub.3-C.sub.30cycloalkylene, --O--,
--S--, --NR.sub.23--, --(CO)--, --O(CO)--, --S(CO)--,
--NR.sub.23(CO)--, --SO--, --SO.sub.2--, --OSO.sub.2-- or
--Ar.sub.2--; optionally the radicals C.sub.1-C.sub.18alkyl and
C.sub.2-C.sub.18alkyl are substituted by one or more
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.11 is C.sub.3-C.sub.30cycloalkyl,
optionally interrupted by one or more --O--, --S--, --NR.sub.23--,
--(CO)--, --O(CO)--, or --NR.sub.23(CO)--, and optionally
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; or R.sub.11 is hydrogen,
C.sub.1-C.sub.8haloalkyl, --Ar.sub.1, --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22 or --SO.sub.2R.sub.19; or
R.sub.10 and R.sub.11 together form a 5-, 6- or 7-membered ring
which optionally is substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or said 5-, 6- or 7-membered ring is
substituted by halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; and said 5-, 6- or 7-membered ring
optionally additionally is interrupted by C.sub.1-C.sub.12alkylene,
C.sub.3-C.sub.30cycloalkylene, C.sub.1-C.sub.8haloalkylene,
C.sub.2-C.sub.12alkenylene, C.sub.4-C.sub.30cycloalkenylene,
phenylene, naphthalene, --O--, --S--, --NR.sub.23--, --(CO)--,
--O(CO)--, --NR.sub.23(CO)--, --S(CO)--, --SO--, --SO.sub.2--, or
--OSO.sub.2--; and to said 5-, 6- or 7-membered ring optionally are
fused one or more benzo radicals; with the provisos that, (1) if h
is 2, X' is -X.sub.1-A.sub.3-X.sub.2- and X.sub.1, X.sub.2 and
A.sub.3 all are a direct bond, then R.sub.10 and R.sub.11 do not
form a ring interrupted by --CO--; (2) if X.sub.0 is
--CH.dbd.CH.sub.2 and R.sub.11 is methyl, then R.sub.10 is not
phenyl or naphthyl; and (3) if X.sub.0 is --CH.dbd.CH.sub.2 or if
X.sub.0 is --[CH.sub.2].sub.h--X, X is OR.sub.20 and R.sub.20 is
methyl, then R.sub.10 and R.sub.11, together do not form 5-, 6- or
7-membered rings which are interrupted by --CO--; R.sub.12,
R.sub.13, R.sub.14 and R.sub.15 independently of each other are
hydrogen, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or R.sub.12, R.sub.13, R.sub.14 and R.sub.15
are halogen, --NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19; optionally the substituents R.sub.12,
R.sub.13, R.sub.14 and/or R.sub.15 form 5-, 6- or 7-membered rings
or fused rings, via the radicals R.sub.12, R.sub.13, R.sub.14
and/or R.sub.15 with further substituents on the phenyl to which
R.sub.12, R.sub.13, R.sub.14 and R.sub.15 are bonded, or with one
of the carbon atoms of said phenyl ring; wherein all radicals
radicals R.sub.12, R.sub.13, R.sub.14 and/or R.sub.15 with the
exception of hydrogen optionally additionally are substituted by a
group having a --O--C-bond or a --O--Si-bond which cleaves upon the
action of an acid; R.sub.16, R.sub.17 and R.sub.18 independently of
each other are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl;
C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; or
R.sub.16, R.sub.17 and R.sub.18 are halogen, --NO.sub.2, --CN,
--Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents R.sub.16,
R.sub.17, and/or R.sub.18 form 5-, 6- or 7-membered rings or fused
rings, via the radicals R.sub.16, R.sub.17, and/or R.sub.18 with
further substituents on the phenyl ring to which R.sub.16, R.sub.17
and R.sub.18 are bonded or with one of the carbon atoms of said
phenyl ring; wherein all radicals radicals R.sub.16, R.sub.17,
and/or R.sub.18 with the exception of hydrogen optionally
additionally are substituted by a group having a --O--C-bond or a
--O--Si-bond which cleaves upon the action of an acid; with the
proviso that (4) R.sub.16, R.sub.17 and R.sub.18 are not all
simultaneously hydrogen, if X.sub.0 is --CH.dbd.CH.sub.2; R.sub.19
is phenyl, naphthyl, C.sub.3-C.sub.30cycloalkyl,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.2-C.sub.12alkenyl, C.sub.4-C.sub.30cycloalkenyl; or is
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--; or
is C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; all
of which optionally are substituted by one or more Ar.sub.1, OH,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.19 is hydrogen; R.sub.20 is phenyl,
naphthyl, C.sub.3-C.sub.30cycloalkyl, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.12alkenyl,
C.sub.4-C.sub.30cycloalkenyl; or is C.sub.2-C.sub.18alkyl which is
interrupted by one or more --O--; or is C.sub.3-C.sub.30cycloalkyl
which is interrupted by one or more --O--, --S--, --NR.sub.23--,
--O(CO)-- or --NR.sub.23(CO)--; or is C.sub.2-C.sub.18alkanoyl, or
is benzoyl, or is C.sub.1-C.sub.18alkylsulfonyl, all of which
optionally are substituted by one or more Ar.sub.1, OH,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.20 is hydrogen, phenylsulfonyl,
(4-methylphenyl)sulfonyl, naphthylsulfonyl, anthracylsulfonyl or
phenanthrylsulfonyl; R.sub.21, R.sub.22 and R.sub.23 independently
of each other are phenyl, naphthyl, C.sub.3-C.sub.30cycloalkyl,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.2-C.sub.12alkenyl, C.sub.4-C.sub.30cycloalkenyl; or are
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--; or
are C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; or
are C.sub.2-C.sub.18alkanoyl, benzoyl or
C.sub.1-C.sub.18alkylsulfonyl, all of which optionally are
substituted by one or more Ar.sub.1, OH, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl,
phenylthio, phenylthiocarbonyl, --NR.sub.21R.sub.22,
C.sub.1-C.sub.12alkylthio, C.sub.2-C.sub.12alkoxycarbonyl,
C.sub.2-C.sub.8haloalkanoyl, halobenzoyl,
C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.21, R.sub.22 and R.sub.23
independently of each other are hydrogen, phenylsulfonyl,
(4-methylphenyl)sulfonyl, naphthylsulfonyl, anthracylsulfonyl or
phenanthrylsulfonyl; or R.sub.21 and R.sub.22, together with the
nitrogen atom to which they are attached, form a 5-, 6- or
7-membered ring which optionally is interrupted by --O-- or by
--NR.sub.23--; with the provisos that (5) if m is 1, X.sub.0 is
--[CH.sub.2].sub.h--X, X is OR.sub.20 or NR.sub.21R.sub.22 and
R.sub.20 is hydrogen, or R.sub.21, and R.sub.22 both are hydrogen,
then R.sub.1 and R.sub.2 are not both simultaneously p-tolyl or
p-chlorophenyl; (6) if m is 0, X.sub.0 is --[CH.sub.2].sub.h--X, X
is NR.sub.21R.sub.22 and R.sub.21 and R.sub.22 both are the same
and are alkyl, which is interrupted by 0, then R.sub.1 is not
thienyl; (7) if X.sub.0 is --[CH.sub.2].sub.h--X, X is OR.sub.20,
R.sub.20 is ethyl and R.sub.8 and R.sub.9 both are hydrogen, then
R.sub.7 is not propyl; (8) if X.sub.0 is --CH.dbd.CH.sub.2, R.sub.8
and R.sub.9 both are hydrogen, n is 1, R.sub.7 is NR.sub.21R.sub.22
and R.sub.21 is hydrogen, then R.sub.22 is not n-C.sub.3H.sub.7,
i-C.sub.3H.sub.7 or cyclohexyl and R.sub.21 and R.sub.22 are not
both simultaneously alkenyl; R.sub.24 is phenyl, naphthyl,
C.sub.3-C.sub.30cycloalkyl, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.4-C.sub.30cycloalkenyl; or is
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--, or
is C.sub.3-C.sub.30cycloalkyl which is interrupted by one or more
--O--, --S--, --NR.sub.23--, --O(CO)--, or --NR.sub.23(CO)--; all
of which are unsubstituted or substituted by one or more Ar.sub.1,
OH, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8-haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.24 is hydrogen; or R.sub.23 and
R.sub.24 together with the N-atom to which they are attached form a
5-, 6- or 7-membered ring which optionally is interrupted by --CO--
or --O-- and which additionally optionally is fused with one or
more benzo rings; R.sub.25, R.sub.26 and R.sub.27 independently of
each other are hydrogen; or are phenyl or naphthyl, both of which
optionally are substituted by one or more Ar.sub.1, OH,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.25, R.sub.26 and R.sub.27 are
C.sub.3-C.sub.18alkenyl or C.sub.3-C.sub.18alkynyl; or R.sub.25,
R.sub.26 and R.sub.27 are C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkyl which is interrupted by one or more --O--,
and wherein the radicals C.sub.1-C.sub.18alkyl and
C.sub.2-C.sub.18alkyl are optionally substituted by one or more
Ar.sub.1, OH, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C
.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.25 and R.sub.26, if appropriate
together with C.sub.1-C.sub.2alkylene, --O--, --S--, or --CO--,
form a fused ring; or R.sub.25, R.sub.26 and R.sub.27, if
appropriate together with C.sub.1-C.sub.2alkylene, --O--, --S--, or
--CO--, form a 5-, 6-, or 7-membered ring; or R.sub.25, R.sub.26
and R.sub.27 together with the N.sup.+-atom to which they are
bonded forma group
##STR00043##
R.sub.28 and R.sub.29 independently of each other are phenyl which
optionally is substituted by one or more Ar.sub.1, OH,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN,
C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl, phenylthio,
phenylthiocarbonyl, --NR.sub.21R.sub.22, C.sub.1-C.sub.12alkylthio,
C.sub.2-C.sub.12alkoxycarbonyl, C.sub.2-C.sub.8haloalkanoyl,
halobenzoyl, C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.28 and R.sub.29 independently of
each other are C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkyl which
is interrupted by one or more --O--, and wherein the radicals
C.sub.1-C.sub.18alkyl and C.sub.2-C.sub.18alkyl are optionally
substituted by one or more Ar.sub.1, OH, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl,
phenylthio, phenylthiocarbonyl, --NR.sub.21R.sub.22,
C.sub.1-C.sub.12alkylthio, C.sub.2-C.sub.12alkoxycarbonyl,
C.sub.2-C.sub.8haloalkanoyl, halobenzoyl,
C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.28 and R.sub.29, if appropriate
together with C.sub.1-C.sub.2alkylene, --O--, --S--, or --CO--,
form a fused ring; or R.sub.28 and R.sub.29, if appropriate
together with C.sub.1-C.sub.2alkylene, --O--, --S--, or --CO--,
form a 5-, 6- or 7-membered ring; R.sub.30, R.sub.31, R.sub.32 and
R.sub.33 are independently of each other hydrogen, halogen,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkoxy,
C.sub.1-C.sub.8haloalkyl, CN, NO.sub.2, C.sub.2-C.sub.18alkanoyl,
benzoyl, phenyl, --S-phenyl, OR.sub.20, SR.sub.23,
NR.sub.21R.sub.22, C.sub.2-C.sub.6alkoxycarbonyl, phenoxycarbonyl,
S(O).sub.pC.sub.1-C.sub.18alkyl, unsubstituted or
C.sub.1-C.sub.18alkyl-substituted S(O).sub.p--C.sub.6-C.sub.12aryl,
SO.sub.2O--C.sub.1-C.sub.18alkyl, SO.sub.2O--C.sub.6-C.sub.10aryl
or NHCONH.sub.2; R.sub.34 and R.sub.35 independently of each other
have one of the meanings given for R.sub.5; or R.sub.34 and
R.sub.35 together are --CO--NR.sub.23CO--; or R.sub.34 and R.sub.35
together are
--C(R.sub.30).dbd.C(R.sub.31)--C(R.sub.32).dbd.C(R.sub.33)--;
Ar.sub.1 is phenyl, naphthyl, anthracyl, phenanthryl, or
heteroaryl, all of which optionally are substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl; C.sub.3-C.sub.30cycloalkyl which is
interrupted by one or more --O--, --S--, --NR.sub.23--, --O(CO)--,
or --NR.sub.23(CO)--; or are substituted by halogen, --NO.sub.2,
--CN, phenyl, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19, optionally the substituents --(CO)R.sub.19,
--(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19,
--O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19 form 5-, 6- or 7-membered rings, via the
radicals R.sub.19, R.sub.20, R.sub.21, R.sub.22 and/or R.sub.23,
with further substituents on the phenyl, naphthyl, anthracyl,
phenanthryl, or heteroaryl ring or with one of the carbon atoms of
the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring;
Ar.sub.2 is phenylene, naphthylene,
##STR00044##
diphenylene, oxydiphenylene or
##STR00045##
wherein these radicals optionally are substituted by one or more
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.8haloalkyl,
C.sub.3-C.sub.30cycloalkyl, halogen, --NO.sub.2, --CN, --Ar.sub.1,
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --O(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19, optionally the substituents
--(CO)R.sub.19, --(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--O(CO)R.sub.19, --O(CO)OR.sub.20, --(CO)NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.19, --NR.sub.23(CO)OR.sub.20, --OR.sub.20,
--NR.sub.21R.sub.22, --SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19
and/or --OSO.sub.2R.sub.19 form 5-, 6- or 7-membered rings, via the
radicals R.sub.19, R.sub.20, R.sub.21, R.sub.22 and/or R.sub.23,
with further substituents on these radicals or with one of the
carbon atoms of these radicals;
M.sup.+ is
##STR00046##
[0049] Li.sup.+, Na.sup.+, K.sup.+, Cs.sup.+, 1/2Mg.sup.2+,
1/2Ca.sup.2+ or 1/2Ba.sup.2+; L.sup.- is F.sup.-, Cl.sup.-,
Br.sup.-, I.sup.-, HSO.sub.4.sup.-, 1/2SO.sub.4.sup.2-,
NO.sub.3.sup.-,
##STR00047##
ClO.sub.4.sup.-, BF.sub.4.sup.-, PF.sub.6.sup.-, AsF.sub.6.sup.-,
SbF.sub.6.sup.-(R.sub.50SO.sub.2).sub.3C.sup.- or
(R.sub.50SO.sub.2).sub.2N.sup.-; R.sub.36, R.sub.37, R.sub.38 and
R.sub.39 have one of the meanings given for R.sub.25, R.sub.26 and
R.sub.27; R.sub.40, R.sub.41 and R.sub.42 have one of the meanings
given for R.sub.28 and R.sub.29; R.sub.43 and R.sub.44
independently of each other are phenyl, which optionally is
substituted by one or more Ar.sub.1, OH, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, C.sub.1-C.sub.12alkoxy, phenoxy, phenoxycarbonyl,
phenylthio, phenylthiocarbonyl, --NR.sub.21R.sub.22,
C.sub.1-C.sub.12alkylthio, C.sub.2-C.sub.12alkoxycarbonyl,
C.sub.2-C.sub.8haloalkanoyl, halobenzoyl,
C.sub.1-C.sub.12alkylsulfonyl, phenylsulfonyl,
(4-methylphenyl)sulfonyl, C.sub.1-C.sub.12alkylsulfonyloxy,
phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy,
C.sub.2-C.sub.12alkanoyl, C.sub.2-C.sub.12alkanoyloxy, benzoyl
and/or by benzoyloxy; or R.sub.43 and R.sub.44, if appropriate
together with C.sub.1-C.sub.2alkylene, --O--, --S--, or --CO--,
form a fused ring; R.sub.45 is C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, camphoryl, phenyl-C.sub.1-C.sub.3alkyl,
C.sub.3-C.sub.30cycloalkyl, C.sub.4-C.sub.30cycloalkenyl, phenyl,
naphthyl, anthracyl or phenanthryl; all of which optionally are
substituted by one or more C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.8haloalkyl, C.sub.3-C.sub.30cycloalkyl, halogen,
--NO.sub.2, --CN, --Ar.sub.1, --(CO)R.sub.19, --(CO)OR.sub.20,
--(CO)NR.sub.21R.sub.22, --O(CO)R.sub.19, --O(CO)OR.sub.20,
--O(CO)NR.sub.21R.sub.22, --NR.sub.23(CO)R.sub.19,
--NR.sub.23(CO)OR.sub.20, --OR.sub.20, --NR.sub.21R.sub.22,
--SR.sub.23, --SOR.sub.19, --SO.sub.2R.sub.19 and/or
--OSO.sub.2R.sub.19; R.sub.46 and R.sub.47 independently of one
another have one of the meanings given for R.sub.5; or R.sub.46 and
R.sub.47 together are --CO--NR.sub.23--CO-- or
--C(R.sub.30).dbd.C(R.sub.31)--C(R.sub.32).dbd.C(R.sub.33)--;
R.sub.48 and R.sub.49 independently of one another have on of the
meanings given for R.sub.5, or R.sub.48 and R.sub.49 together are
--CO--NR.sub.23--CO-- or
--C(R.sub.30).dbd.C(R.sub.31)--C(R.sub.32).dbd.C(R.sub.33)--;
R.sub.50 is C.sub.1-C.sub.8-perfluoroalkyl;
Q.sub.1 is --CR.sub.35-- or --N--; and
Q.sub.2 is --CH.sub.2--, --S--, --O-- or --NR.sub.23--.
[0050] Sulfonate derivatives of formulae Ia, IIa, IIIa, IVa, Va and
VIa, wherein X.sub.0 is --[CH.sub.2].sub.h--X and compounds of
formula Ib, IIb, IIIb, IVb or Vb, can generally be prepared by
methods described in the literature, for example by reacting
corresponding free alcohols or oximes (R--OH) of said formulae with
chloroalkylsulfonyl chlorides in the presence of bases, followed by
the reaction with nucleophiles (e.g. X--H, X--Na for example
described in, Angew. Chem. Int. Ed. 1965, 4, 300) or with suitable
sulfonyl chlorides.
##STR00048##
[0051] The reaction of free oximes or alcohols (R--OH) with
sulfonyl chlorides mentioned above is usually carried out in
aprotic solvents such as for example toluene, methylene chloride,
tetrahydrofuran (THF), acetone, or dimethylformamide (DMF) in the
presence of a base, for example, pyridine, a tertiary amine, such
as triethylamine, or by reacting the salt of an oxime or alcohol
with the desired sulfonyl chloride. These methods are disclosed,
for example, in EP 48615. The sodium salts of oximes can be
obtained, for example, by reacting the oxime in question with a
sodium alkoxide in dimethylformamide. Such reactions are well known
to those skilled in the art, and are generally carried out at
temperatures in the range of -15 to +50.degree. C., preferably
0.degree. C. to 20.degree. C. The succeeding reaction with
nucleophiles can be conducted in, for example, aprotic solvents
mentioned above or protic solvents such as for example water,
methanol, ethanol, or 2-propanol. Nucleophiles such as, for
example, free alcohols, thiols, primary or secondary amines (X--H)
can be added together with bases such as for example tertiary
amines like triethylamine or pyridine, or sodium or potassium salts
(X--Na, X--K) of nucleophiles such as alkoxides, thiolates,
sulfinic acid salts, sulfonic acid salts, carboxylic acid salts,
amides, or imides can be employed. Such reactions are well known to
those skilled in the art, and are usually carried out at
temperatures in the range of -80 to +150.degree. C., preferably -20
to 80.degree. C.
[0052] Chloroalkylsulfonyl chlorides are commercially available or
can generally be prepared by methods described in the literature,
for example by reacting halogenated alcohols with Na.sub.2SO.sub.3
or NaHSO.sub.3, followed by treatment with PCl.sub.5 or thionyl
chloride as is for example described in Chem. Ber. 1955, 88, 201,
or by reacting .alpha.,.omega.-dihaloalkane with Na.sub.2SO.sub.3
or Na--HSO.sub.3 as for example described in Org. Syn., 1943, II,
558, followed by treatment with PCl.sub.5 or thionyl chloride. The
suitable sulfonyl chlorides described above
(X(CH.sub.2).sub.hSO.sub.2Cl) can be prepared by methods described
in the literature, for example by reacting chloroalkylsulfonic
acids or their salts with nucleophiles (X--H, X--Na), followed by
reaction with PCl.sub.5 or thionyl chloride, or by reacting
1,3-propane sultone with nucleophiles (X--H, X--Na), followed by
reaction with PCl.sub.5 or thionyl chloride as is for example
described in Industrial and Engineering Chemistry, 1964, 56, 41,
and Chem. Ber. 1955, 88, 201. These reactions are well known to
those skilled in the art.
[0053] Sulfonate derivatives of formulae Ia, IIa, IIIa, IVa, Va and
VIa, wherein X.sub.0 is --CH.dbd.CH.sub.2, can generally be
prepared by methods described in the literature, for example by
reacting corresponding free alcohols or oximes (R--OH) of said
formulae with 2-chloroethanesulfonyl chloride in the presence of
bases as for example described in Angew. Chem. Int. Ed. 1965, 4,
300.
##STR00049##
[0054] This reaction of free oximes or alcohols (R--OH) with
2-chloroethanesulfonyl chloride mentioned above is usually carried
out in aprotic solvents such as for example toluene, methylene
chloride, tetrahydrofuran (THF), acetone, or dimethylformamide
(DMF) in the presence of a base, for example, pyridine, a tertiary
amine, such as triethylamine, or by reacting the salt of an oxime
or alcohol with the desired sulfonyl chloride. Such reactions are
well known to those skilled in the art, and are generally carried
out at temperatures in the range of -15.degree. C. to +50.degree.
C., preferably 0.degree. C. to 20.degree. C.
[0055] Corresponding free oximes and alcohols (R--OH) are
commercially available or can be pre-pared according to the
procedures described in, for example, U.S. Pat. No. 6,004,724, WO
00/10972, GB 2348644, U.S. Pat. No. 4,540,598. These reactions are
well known to those skilled in the art.
[0056] The syntheses of oximes can result in the formation of
isomeric forms of the compounds of formula Ia, Ib, IIa and IIb. The
double bond of the oximino group can exist in both the syn (cis, Z)
and the anti (trans, E) form or as mixtures of the two geometrical
isomers. In the present invention, both the individual geometrical
isomers and any mixtures of two geometrical isomers can be used.
The invention accordingly also relates to mixtures of isomeric
forms of the compounds of formula Ia, Ib, IIa and IIb. If wanted
the isomeric compounds can be separated by the usual methods known
to the person skilled in the art.
[0057] Interesting are compounds of the formula Ia, Ib, IIa and/or
IIb, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
X, X', m, n, h and G are as defined above.
[0058] Interesting are further compounds of the formula Ia, Ib, IIa
and/or IIb, wherein
m is 0; R.sub.2 is C.sub.1-C.sub.8haloalkyl or --CN;
R.sub.4 is --CN;
[0059] G is S or a group of formula Z.sub.1; R.sub.1, R.sub.3,
R.sub.5, R.sub.6, X, X', n, h, Q.sub.1 and R.sub.34 are as defined
above.
[0060] Other interesting compounds are of the formula Ia, Ib, IIa,
IVa wherein
n is 1 or 2; m is 0; h is 2; R.sub.1 when n is 1 is phenyl
optionally substituted by C.sub.1-C.sub.4alkyl or OR.sub.20;
R.sub.1 when n is 2 is
##STR00050##
A.sub.1 is a direct bond or --O--; A.sub.2 is
C.sub.1-C.sub.4alkylene;
A.sub.3 is -A.sub.1-A.sub.2-A.sub.1-;
[0061] R.sub.2 is C.sub.1-C.sub.4haloalkyl; R.sub.3 is phenyl
optionally substituted by C.sub.1-C.sub.4alkyl;
R.sub.4 is CN;
X is --OR.sub.20, SR.sub.23, NR.sub.21R.sub.22,
--NR.sub.23(CO)R.sub.24, SO.sub.2R.sub.19 or
##STR00051##
[0062] X.sub.1 and X.sub.2 are --S--;
[0063] R.sub.20 is C.sub.1-C.sub.4alkyl, or is C.sub.2-C.sub.8alkyl
which is interrupted by --O--; R.sub.21, R.sub.22 and R.sub.23 are
C.sub.1-C.sub.4-Alkyl, which optionally is substituted by OH; or
R.sub.23 and R.sub.24 together with the N-atom to which they are
attached form a 5-membered ring which is interrupted by --CO-- and
to which a benzo ring is fused; R.sub.25, R.sub.26 and R.sub.27
together with the N.sup.+-atom to which they are bonded form a
group
##STR00052##
Ar.sub.1 is phenyl which optionally is substituted by
C.sub.1-C.sub.4alkyl or OR.sub.20;
L.sup.- is SO.sub.3R.sub.45;
[0064] R.sub.45 is C.sub.1-C.sub.8haloalkyl; and R.sub.46 and
R.sub.47 are hydrogen.
[0065] Further interesting are compounds of the formula Ia,
wherein
n is 1 or 2; m is 0; h is 2; R.sub.1 when n is 1 is phenyl
optionally substituted by C.sub.1-C.sub.4alkyl or OR.sub.20;
R.sub.1 when n is 2 is -A.sub.1-A.sub.2-A.sub.1-;
A.sub.1 is --O--;
[0066] A.sub.2 is C.sub.1-C.sub.4alkylene; R.sub.2 is
C.sub.1-C.sub.4haloalkyl;
X is --OR.sub.20, SR.sub.23 or --NR.sub.23(CO)R.sub.24;
[0067] R.sub.20 is C.sub.1-C.sub.4alkyl, or is C.sub.2-C.sub.8alkyl
which is interrupted by --O--; R.sub.21, R.sub.22 and R.sub.23 are
C.sub.1-C.sub.4-Alkyl, which optionally is substituted by OH; or
R.sub.23 and R.sub.24 together with the N-atom to which they are
attached form a 5-membered ring which is interrupted by --CO-- and
to which a benzo ring is fused; and Ar.sub.1 is phenyl which
optionally is substituted by C.sub.1-C.sub.4alkyl or OR.sub.20.
[0068] The compounds of the formulae Ia, Ib, IIa, IIb, IIIa, IIIb,
IVa, IVb, Va, Vb and VIa can be used as photosensitive acid donors
in a photoresist. Resist systems can be prepared by image-wise
irradiation of systems comprising compounds of formulae Ia, Ib,
IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb, or VIa, followed by a
developing step.
[0069] A chemically amplified photoresist is understood to be a
resist composition wherein the radiation sensitive component
provides a catalytic amount of acid which subsequently catalyses a
chemical reaction of at least one acid-sensitive component of the
resist. Resulting is the induction of a solubility difference
between the irradiated and non-irradiated areas of the resist.
Because of the catalytic nature of this process one acid molecule
can trigger reactions at multiple sites as it diffuses through the
reactive polymer matrix, from one reaction site to the next, as
long as it is not trapped or destroyed by any secondary reaction.
Therefore, a small acid concentration is sufficient to induce a
high difference in the solubility between exposed and unexposed
areas in the resist. Thus, only a small concentration of the latent
acid compound is necessary. As a result, resists with high contrast
and high transparency at the exposure wavelength in optical imaging
can be formulated, which in turn produce steep, vertical image
profiles at high photosensitivity. However, as a result of this
catalytic process, it is required that the latent acid catalysts
are chemically and thermally very stable (as long as not
irradiated) in order not to generate acid during resist storage or
during processing, which--in most cases--requires a post exposure
bake step to start or to complete the catalytic reaction which
leads to the solubility differential. It is also required to have
good solubility of the latent catalysts in the liquid resist
formulation and the solid resist film to avoid any particle
generation which would interfere with the application of these
resists in microelectronic manufacturing processes.
[0070] In contrast, positive resist materials which are not based
on the chemical amplification mechanism must contain a high
concentration of the latent acid, because it is only the acid
concentration which is generated from the latent acid under
exposure which contributes to the increased solubility of the
exposed areas in alkaline developer. Because small acid
concentration has only a little effect on the change of the
dissolution rate of such resist and the reaction proceeds typically
without a post exposure bake here, the requirements regarding
chemical and thermal stability of the latent acid are less
demanding than for chemically amplified positive resists. These
resists require also a much higher exposure dose to generate enough
acid for achieving sufficient solubility in the alkaline developer
in the exposed areas and also suffer from the relatively low
optical transparency (due to the high concentration of latent acid
necessary) and thus also lower resolution and sloped images. Resist
compositions based on non-chemically amplified technology are
therefore inferior in photosensitivity, resolution and image
quality compared to chemically amplified resists.
[0071] From the above it becomes clear that chemical and thermal
stability of a latent catalyst is vital for a chemically amplified
resist and that latent acids which can work in a non-chemically
amplified resist are not necessarily applicable to chemically
amplified resists because of the different acid diffusion
requirements, acid strength requirements and thermal and chemical
stability requirements.
[0072] The difference in resist solubility between irradiated and
non-irradiated sections that occurs as a result of the
acid-catalysed reaction of the resist material during or after
irradiation of the resist may be of two types depending upon which
further constituents are present in the resist. If the compositions
according to the invention comprise components that increase the
solubility of the composition in the developer after irradiation,
the resist is positive.
[0073] The invention accordingly relates to a chemically amplified
positive photoresist.
[0074] If, on the other hand, the components of the formulation
reduce the solubility of the composition after irradiation, the
resist is negative.
[0075] The invention accordingly relates also to a chemically
amplified negative photoresist.
[0076] A monomeric or polymeric compound which--in the unexposed
areas--reduces the dissolution rate of an additionally present
alkaline soluble binder resin in the resist formulation and which
is essentially alkali-insoluble in the unexposed areas so that the
resist film remains in the unexposed area after development in
alkaline solution, but which is cleaved in the presence of acid, or
is capable of being rearranged, in such a manner that its reaction
product becomes soluble in the alkaline developer is referred to
hereinafter as dissolution inhibitor.
[0077] The invention includes, as a special embodiment a chemically
amplified positive alkaline-developable photoresist composition,
comprising
(a1) at least one polymer having acid-labile groups which decompose
in the presence of an acid and increase the solubility of the
resist film in an aqueous alkaline developer solution in the
exposed area and (b) at least one compound of formula Ia, Ib, IIa,
IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa.
[0078] A further embodiment of the invention is a chemically
amplified positive alkaline-developable photoresist composition,
comprising
(a2) at least one monomeric or oligomeric dissolution inhibitor
having at least one acid-labile group which decomposes in the
presence of acid and increases the solubility in an aqueous
alkaline developer solution and at least one alkali-soluble polymer
and, (b) at least one compound of formula Ia, Ib, IIa, IIb, IIIa,
IIIb, IVa, IVb, Va, Vb or VIa. Another specific embodiment of the
invention resides in a chemically amplified positive
alkaline-developable photoresist composition, comprising (a1) at
least one polymer having acid labile groups which decompose in the
presence of an acid and increase the solubility in an alkaline
developer in the exposed area; (a2) a monomeric or oligomeric
dissolution inhibitor, having at least one acid labile group, which
decomposes in the presence of an acid and increase the alkaline
solubility in the exposed area; (a3) an alkali-soluble monomeric,
oligomeric or polymeric compound at a concentration which still
keeps the resist film in the unexposed area essentially insoluble
in the alkaline developer, and (b) at least one compound of formula
Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa.
[0079] The invention therefore pertains to a chemically amplified
photoresist composition, comprising
(a1) at least one polymer having an acid-labile group which
decomposes in the presence of an acid to increase the solubility in
aqueous alkaline developer solution and/or (a2) at least one
monomeric or oligomeric dissolution inhibitor having an acid-labile
group which decomposes in the presence of an acid to increase the
solubility in aqueous alkaline developer solution and/or (a3) at
least one alkali-soluble monomeric, oligomeric or polymeric
compound; and (b) as photosensitive acid donor, at least one
compound of formula Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb
or VIa.
[0080] The compositions may comprise additionally to the component
(b) other photosensitive acid donors and/or (c) other
additives.
[0081] Such chemically amplified positive resist systems are
described, for example, in E. Reichmanis, F. M. Houlihan, O.
Nalamasu, T. X. Neenan, Chem. Mater. 1991, 3, 394; or in C. G.
Willson, "Introduction to Microlithography, 2nd. Ed.; L. S.
Thompson, C. G. Willson, M. J. Bowden, Eds., Amer. Chem. Soc.,
Washington D.C., 1994, p. 139.
[0082] Suitable examples of acid-labile groups which decompose in
the presence of an acid to produce aromatic hydroxy groups,
carboxylic groups, keto groups and aldehyde groups and increase the
solubility in aqueous alkaline developer solution are, for example,
alkoxyalkyl ether groups, tetrahydrofuranyl ether groups,
tetrahydropyranyl ether groups, tert.-alkyl ester groups, trityl
ether groups, silyl ether groups, alkyl carbonate groups as for
example tert.-butyloxycarbonyloxy-, trityl ester groups, silyl
ester groups, alkoxymethyl ester groups, cumyl ester groups, acetal
groups, ketal groups, tetrahydropyranyl ester groups, tetrafuranyl
ester groups, tertiary alkyl ether groups, tertiary alkyl ester
groups, and the like.
[0083] The polymer having functional groups capable of decomposing
by the action of an acid to enhance solubility of the resist film
comprising this polymer in an alkaline developing solution, which
can be incorporated in the positive resist according to the present
invention, may have the acid-labile groups in the backbone and/or
side chains thereof, preferably in side chains thereof.
[0084] The polymer having acid-labile groups suitable for the use
in the present invention can be obtained with a polymer analogous
reaction where the alkaline soluble groups are partially or
completely converted into the respective acid labile groups or
directly by (co)-polymerization of monomers which have the acid
labile groups already attached, as is for instance disclosed in EP
254853, EP 878738, EP 877293, JP-A-2-25850, JP-A-3-223860, and
JP-A-4-251259.
[0085] The polymers which have acid labile groups pendant to the
polymer backbone, in the pre-sent invention preferably are polymers
which have, for example silylether, acetal, ketal and
alkoxyalkylester groups (called "low-activation energy blocking
groups") which cleave completely at relatively low post exposure
bake temperatures (typically between room temperature and
110.degree. C.) and polymers which have, for example,
tert-butylester groups or tert.-butyloxycarbonyl (TBOC) groups or
other ester groups which contain a secondary or tertiary carbon
atom next to the oxygen atom of the ester bond (called
"high-activation energy blocking groups") which need higher bake
temperatures (typically >110.degree. C.) in order to complete
the deblocking reaction in the presence of acid. Hybrid systems can
also be applied, wherein, both, high activation energy blocking
groups as well as low activation energy blocking groups are present
within one polymer. Alternatively, polymer blends of polymers, each
utilizing a different blocking group chemistry, can be used in the
photosensitive positive resist compositions according to the
invention.
[0086] Preferred polymers which have acid labile groups are
polymers and co-polymers comprising the following distinct monomer
types:
1) monomers that contain acid-labile groups which decompose in the
presence of an acid to increase the solubility in aqueous alkaline
developer solution and 2) monomers that are free of acid labile
groups and free of groups that contribute to the alkaline
solubility and/or 3) monomers that contribute to aqueous alkaline
solubility of the polymer.
[0087] Examples of monomers of type 1) are:
non-cyclic or cyclic secondary and tertiary-alkyl (meth)acrylates
such as butyl acrylate, including t-butyl acrylate, butyl
methacrylate, including t-butyl methacrylate, 3-oxocyclohexyl
(meth)acrylate, tetrahydropyranyl (meth)acrylate,
2-methyl-adamantyl (meth)acrylate, cyclohexyl (meth)acrylate,
norbornyl (meth)acrylate, (2-tetrahydropyranyl)oxynorbonylalcohol
acrylates, (2-tetrahydropyranyl)oxymethyltricyclododecanemethanol
methacrylates, trimethylsilylmethyl (meth)acrylate,
(2-tetrahydropyranyl)oxynorbonylalcohol acrylates,
(2-tetrahydropyranyl)oxymethyltricyclododecanemethanol
methacrylates, trimethylsilylmethyl (meth)acrylate
o-/m-/p-(3-oxocyclohexyloxy)styrene,
o-/m-/p-(1-methyl-1-phenylethoxy)styrene,
o-/m-/p-tetrahydropyranyloxystyrene, o-/m-/p-adamantyloxystyrene,
o-/m-/p-cyclohexyloxystyrene, o-/m-/p-norbornyloxystyrene,
non-cyclic or cyclic alkoxycarbonylstyrenes such as
o-/m-/p-butoxycarbonylstyrene, including p-t-butoxycarbonylstyrene,
o-/m-/p-(3-oxocyclohexyloxycarbonyl)-styrene,
o-/m-/p-(1-methyl-1-phenylethoxycarbonyl)styrene,
o-/m-/p-tetrahydropyranyloxycarbonylstyrene,
o-/m-/p-adamantyloxycarbonylstyrene,
o-/m-/p-cyclohexyloxycarbonylstyrene,
o-/m-/p-norbornyloxycarbonylstyrene, non-cyclic or cyclic
alkoxycarbonyloxystyrenes such as o-/m-/p-butoxycarbonyloxystyrene,
including p-t-butoxycarbonyloxystyrene,
o-/m-/p-(3-oxocyclohexyloxycarbonyloxy)styrene,
o-/m-/p-(1-methyl-1-phenylethoxycarbonyloxy)-styrene,
o-/m-/p-tetrahydropyranyloxycarbonyloxystyrene,
o-/m-/p-adamantyloxycarbonyloxystyrene,
o-/m-/p-cyclohexyloxycarbonyloxystyrene,
o-/m-/p-norbornyloxycarbonyloxystyrene, non-cyclic or cyclic
alkoxycarbonylalkoxystyrenes such
aso/m/p-butoxycarbonylmethoxystyrene,
p-t-butoxycarbonylmethoxystyrene,
o-/m-/p-(3-oxocyclohexyloxycarbonylmethoxy)-styrene,
o-/m-/p-(1-methyl-1-phenylethoxycarbonylmethoxy)styrene,
o-/m-/p-tetrahydropyranyloxycarbonylmethoxystyrene,
o-/m-/p-adamantyloxycarbonylmethoxystyrene,
o-/m-/p-cyclohexyloxycarbonylmethoxystyrene,
o-/m-/p-norbornyloxycarbonylmethoxystyrene, trimethylsiloxystyrene,
dimethyl(butyl)siloxystyrene, unsaturated alkyl acetates such as
isopropenyl acetate and the derivatives of thereof.
[0088] Monomers of type 1) bearing low activation energy acid
labile groups include, for example, p- or
m-(1-methoxy-1-methylethoxy)-styrene, p- or
m-(1-methoxy-1-methylethoxy)-methylstyrene, p- or
m-(1-methoxy-1-methylpropoxy)styrene, p- or
m-(1-methoxy-1-methylpropoxy)methylstyrene, p- or
m-(1-methoxyethoxy)-styrene, p- or
m-(1-methoxyethoxy)-methylstyrene, p- or
m-(1-ethoxy-1-methylethoxy)styrene, p- or
m-(1-ethoxy-1-methylethoxy)-methylstyrene, p- or
m-(1-ethoxy-1-methylpropoxy)styrene, p- or
m-(1-ethoxy-1-methylpropoxy)-methylstyrene, p- or
m-(1-ethoxyethoxy)styrene, p- or m-(1-ethoxyethoxy)-methylstyrene,
p-(1-ethoxyphenyl-ethoxy)styrene, p- or
m-(1-n-propoxy-1-methylethoxy)styrene, p- or
m-(1-n-propoxy-1-methylethoxy)-methylstyrene, p- or
m-(1-n-propoxyethoxy)styrene, p- or
m-(1-n-propoxyethoxy)-methylstyrene, p- or
m-(1-isopropoxy-1-methylethoxy)styrene, p- or
m-(1-isopropoxy-1-methylethoxy)-methylstyrene, p- or
m-(1-isopropoxyethoxy)styrene, p- or
m-(1-isopropoxyethoxy)-methylstyrene, p- or
m-(1-isopropoxy-1-methylpropoxy)styrene, p- or
m-(1-isopropoxy-1-methylporpoxy)-methylstyrene, p- or
m-(1-isopropoxypropoxy)styrene, p- or
m-(1-isopropoxyporpoxy)-methylstyrene, p- or
m-(1-n-butoxy-1-methylethoxy)styrene, p- or
m-(1-n-butoxyethoxy)styrene, p- or
m-(1-isobutoxy-1-methylethoxy)styrene, p- or
m-(1-tert-butoxy-1-methylethoxy)styrene, p- or
m-(1-n-pentoxy-1-methylethoxy)styrene, p- or
m-(1-iso-amyloxy-1-methylethoxy)styrene, p- or
m-(1-n-hexyloxy-1-methylethoxy)styrene, p- or
m-(1-cyclohexyloxy-1-methylethoxy)styrene, p- or
m-(1-trimethylsilyloxy-1-methylethoxy)styrene, p- or
m-(1-trimethylsilyloxy-1-methylethoxy)-methylstyrene, p- or
m-(1-benzyloxy-1-methylethoxy)styrene, p- or
m-(1-benzyloxy-1-methylethoxy)-methylstyrene, p- or
m-(1-methoxy-1-methylethoxy)styrene, p- or
m-(1-methoxy-1-methylethoxy)-methylstyrene, p- or
m-(1-trimethylsilyloxy-1-methylethoxy)styrene p- or
m-(1-trimethylsilyloxy-1-methylethoxy)-methylstyrene. Other
examples of polymers having alkoxyalkylester acid labile groups are
given in U.S. Pat. No. 5,225,316 and EP 829766. Examples of
polymers with acetal blocking groups are given in U.S. Pat. No.
5,670,299, EP 780732, U.S. Pat. No. 5,627,006, U.S. Pat. No.
5,558,976, U.S. Pat. No. 5,558,971, U.S. Pat. No. 5,468,589, EP
704762, EP 762206, EP 342498, EP 553737 and described in ACS Symp.
Ser. 614, Microelectronics Technology, pp. 35-55 (1995) and J.
Photopolymer Sci. Technol. Vol. 10, No. 4 (1997), pp. 571-578. The
polymer used in the present invention is not limited thereto.
[0089] With respect to polymers having acetal groups as acid-labile
groups, it is possible to incorporate acid labile crosslinks as for
example described in H.-T. Schacht, P. Falcigno, N. Muenzel, R.
Schulz, and A. Medina, ACS Symp. Ser. 706 (Micro- and
Nanopalterning Polymers), p. 78-94, 1997; H.-T. Schacht, N.
Muenzel, P. Falcigno, H. Holzwarth, and J. Schneider, J.
Photopolymer Science and Technology, Vol. 9, (1996), 573-586. This
crosslinked system is preferred from the standpoint of heat
resistance of the resist patterns.
[0090] Monomers with high activation energy acid labile groups are,
for example, p-tert.-butoxycarbonyloxystyrene,
tert.-butyl-acrylate, tert.-butyl-methacrylate,
2-methyl-2-adamantyl-methacrylate, isobornyl-methacrylate.
[0091] Examples of comonomers according to type 2) are:
aromatic vinyl monomers, such as styrene, .alpha.-methylstyrene,
acetoxystyrene, .alpha.-methylnaphthylene, acenaphthylene, vinyl
alicyclic compounds such as vinyl norbornane, vinyl adamantane.
vinyl cyclohexane, alkyl (meth)acrylates such as methyl
methacrylate, acrylonitrile, vinylcyclohexane, vinylcyclohexanol,
as well as maleic anhydride.
[0092] Examples of comonomers according to type 3) are:
vinyl aromatic compounds such as hydroxystyrene, acrylic acid
compounds such as methacrylic acid, ethylcarbonyloxystyrene and
derivatives of thereof. These polymers are described, for example,
in U.S. Pat. No. 5,827,634, U.S. Pat. No. 5,625,020, U.S. Pat. No.
5,492,793, U.S. Pat. No. 5,372,912, EP 660187, U.S. Pat. No.
5,679,495, EP 813113 and EP 831369. Further examples are crotonic
acid, isocrotonic acid, 3-butenoic acid, acrylic acid, 4-pentenoic
acid, propiolic acid, 2-butynoic acid, maleic acid, fumaric acid,
and acetylenecarboxylic acid. The polymer used in the present
invention is not limited thereto.
[0093] The content of acid labile monomers in the polymer may vary
over a wide range and depends on the amount of the other comonomers
and the alkaline solubility of the deprotected polymer. Typically,
the content of monomers with acid labile groups in the polymer is
between 5 and 60 mol %. If the content is too small, too low
development rates and residues of the resist in the exposed areas
result. If the content of acid labile monomers is too high, resist
patterns are poorly defined (eroded) after development and narrow
features cannot be resolved anymore and/or the resist looses its
adhesion to the substrate during development. Preferably the
copolymers which have acid labile groups have a M.sub.W of from
about 3'000 to about 200'000, more preferably from about 5'000 to
about 50'000 with a molecular weight distribution of about 3 or
less, more preferably a molecular weight distribution of about 2 or
less. Non-phenolic polymers, e.g. a copolymer of an alkyl acrylate
such as t-butyl acrylate or t-butyl-methacrylate and a vinyl
alicyclic compound, such as a vinyl norbonanyl or vinyl
cyclohexanol compound, also may be prepared by such free radical
polymerization or other known procedures and suitably will have a
M.sub.W of from about 8'000 to about 50'000, and a molecular weight
distribution of about 3 or less.
[0094] Other comonomers may suitably be added in an appropriate
amount for the purpose of controlling the glass transition point of
the polymer and the like.
[0095] In the present invention a mixture of two or more polymers
having acid-labile groups may be used. For example, use may be made
of a mixture of a polymer having acid-labile groups, which are
cleaved very easily, such as acetal groups or
tetrahydropyranyloxy-groups and a polymer having acid-cleavable
groups, that are less easily cleaved, such as for example tertiary
alkyl ester groups. Also, acid cleavable groups of different size
can be combined by blending two or more polymers having different
acid cleavable groups, such as a tert-butylester group and
2-methyl-adamantyl group or an 1-ethoxy-ethoxy group and a
tetrahydropyranyloxy group. A mixture of a non-crosslinked resin
and a crosslinked resin may also be used. The amount of these
polymers in the present invention is preferably from 30 to 99% by
weight, more preferably from 50 to 98% by weight, based on the
total amount of all solid components. An alkali-soluble resin or
monomeric or oligomeric compound having no acid-labile groups may
be further incorporated into the composition in order to control
the alkali solubility.
[0096] Examples of polymer blends with polymers having different
acid-labile groups are given in EP 780732, EP 679951 and U.S. Pat.
No. 5,817,444.
[0097] Preferably monomeric and oligomeric dissolution inhibitors
(a2) are used in the present invention.
[0098] The monomeric or oligomeric dissolution inhibitor having the
acid-labile group for use in the present invention is a compound
which has at least one acid-labile group in the molecular
structure, which decomposes in the presence of acid to increase the
solubility in aqueous alkaline developer solution. Examples are
alkoxymethyl ether groups, tetrahydrofuranyl ether groups,
tetrahydropyranyl ether groups, alkoxyethyl ether groups, trityl
ether groups, silyl ether groups, alkyl carbonate groups, trityl
ester groups, silyl ester groups, alkoxymethyl ester groups, vinyl
carbamate groups, tertiary alkyl carbamate groups, trityl amino
groups, cumyl ester groups, acetal groups, ketal groups,
tetrahydropyranyl ester groups, tetrafuranyl ester groups, tertiary
alkyl ether groups, tertiary alkyl ester groups, and the like. The
molecular weight of the acid-decomposable dissolution inhibitive
compound for use in the present invention is 3'000 or lower,
preferably from 100 to 3'000, more preferably from 200 to
2'500.
[0099] Examples of monomeric and oligomeric dissolution inhibitors
having acid-labile groups are described as formulae (I) to (XVI) in
EP 0831369. Other suitable dissolution inhibitors having
acid-labile groups are shown in U.S. Pat. No. 5,356,752, U.S. Pat.
No. 5,037,721, U.S. Pat. No. 5,015,554, JP-A-1-289946,
JP-A-1-289947, JP-A-2-2560, JP-A-3-128959, JP-A-3-158855,
JP-A-3-179353, JP-A-3-191351, JP-A-3-200251, JP-A-3-200252,
JP-A-3-200253, JP-A-3-200254, JP-A-3-200255, JP-A-3-259149,
JA-3-279958, JP-A-3-279959, JP-A-4-1650, JP-A-4-1651, JP-A-11260,
JP-A-4-12356, JP-A-4-123567, JP-A-1-289946, JP-A-3-128959,
JP-A-3-158855, JP-A-3-179353, JP-A-3-191351, JP-A-3-200251,
JP-A-3-200252, JP-A-3-200253, JP-A-3-200254, JP-A-3-200255,
JP-A-3-259149, JA-3-279958, JP-A-3-279959, JP-A-4-1650,
JP-A-4-1651, JP-A-11260, JP-A-4-12356, JP-A-4-12357 and Japanese
Patent Applications Nos. 3-33229, 3-230790, 3-320438, 4-254157,
4-52732, 4-103215, 4-104542, 4-107885, 4-107889, 4-152195,
4-254157, 4-103215, 4-104542, 4-107885, 4-107889, and 4-152195.
[0100] The composition can also contain polymeric dissolution
inhibitors, for example, polyacetals as described for example in
U.S. Pat. No. 5,354,643 or poly-N,O-acetals for example those
described in U.S. Pat. No. 5,498,506, either in combination with an
alkaline soluble polymer, or in combination with a polymer
containing acid labile groups which increase the solubility of the
resist film in the developer after exposure, or with a combination
of both types of polymers.
[0101] In the case where the dissolution inhibitor having
acid-labile groups is used in the present invention in combination
with the sulfonate derivatives of formula Ia, Ib, IIa, IIb, IIIa,
IIIb, IVa, IVb, Va, Vb or VIa, the alkali-soluble polymer and/or
the polymer having acid-labile groups, the amount of the
dissolution inhibitor is from 3 to 55% by weight, preferably from 5
to 45% by weight, most preferably from 10 to 35% by weight, based
on the total amount of all solid components of the photosensitive
composition.
[0102] A polymer soluble in an aqueous alkali solution (a3) is
preferably used in the present invention. Examples of these
polymers include novolak resins, hydrogenated novolak resins,
acetone-pyrogallol resins, poly(o-hydroxystyrene),
poly(m-hydroxystyrene), poly(p-hydroxystyrene), hydrogenated
poly(hydroxystyrene)s, halogen- or alkyl-substituted
poly(hydroxystyrene)s, hydroxystyrene/N-substituted maleimide
copolymers, o/p- and m/p-hydroxystyrene copolymers, partially
o-alkylated poly(hydroxystyrene)s, [e.g., o-methylated,
o-(1-methoxy)ethylated, o-(1-ethoxy)ethylated,
o-2-tetrahydropyranylated, and o-(t-butoxycarbonyl)methylated
poly(hydroxystyrene)s having a degree of substitution of from 5 to
30 mol % of the hydroxyl groups], o-acylated poly(hydroxystyrene)s
[e.g., o-acetylated and o-(t-butoxy)carbonylated
poly(hydroxystyrene)s having a degree of substitution of from 5 to
30 mol % of the hydroxyl groups], styrene/maleic anhydride
copolymers, styrene/hydroxystyrene copolymers,
.alpha.-methylstyrene/hydroxystyrene copolymers, carboxylated
methacrylic resins, and derivatives thereof. Further suitable are
poly (meth)acrylic acid [e.g. poly(acrylic acid)], (meth)acrylic
acid/(meth)acrylate copolymers [e.g. acrylic acid/methyl acrylate
copolymers, methacrylic acid/methyl methacrylate copolymers or
methacrylic acid/methyl methacrylate/t-butyl methacrylate
copolymers], (meth)acrylic acid/alkene copolymers [e.g. acrylic
acid/ethylene copolymers], (meth)acrylic acid/(meth)acrylamide
copolymers [e.g. acrylic acid/acrylamide copolymers], (meth)acrylic
acid/vinyl chloride copolymers [e.g. acrylic acid/vinyl chloride
copolymers], (meth)acrylic acid/vinyl acetate copolymer [e.g.
acrylic acid/vinyl acetate copolymers], maleic acid/vinyl ether
copolymers [e.g. maleic acid/methyl vinyl ether copolymers], maleic
acid mono ester/methyl vinyl ester copolymers [e.g. maleic acid
mono methyl ester/methyl vinyl ether copolymers], maleic
acid/(meth)acrylic acid copolymers [e.g. maleic acid/acrylic acid
copolymers or maleic acid/methacrylic acid copolymers], maleic
acid/(meth)acrylate copolymers [e.g. maleic acid/methyl acrylate
copolymers], maleic acid/-vinyl chloride copolymers, maleic
acid/vinyl acetate copolymers and maleic acid/alkene copolymers
[e.g. maleic acid/ethylene copolymers and maleic
acid/1-chloropropene copolymers]. However, the alkali-soluble
polymer for use in the present invention should not be construed as
being limited to these examples.
[0103] Especially preferred alkali-soluble polymers (a3) are
novolak resins, poly(o-hydroxystyrene), poly(m-hydroxystyrene),
poly(p-hydroxystyrene), copolymers of the respective hydroxystyrene
monomers, for example with p-vinylcyclohexanol, alkyl-substituted
poly(hydroxystyrene)s, partially o- or m-alkylated and o- or
m-acylated poly(hydroxystyrene)s, styrene/hydroxystyrene copolymer,
and .alpha.-methylstyrene/hydroxystyrene copolymers. The novolak
resins are obtained by addition-condensing one or more given
monomers as the main ingredient with one or more aldehydes in the
presence of an acid catalyst.
[0104] Examples of monomers useful in preparing alkaline soluble
resins include hydroxylated aromatic compounds such as phenol,
cresols, i.e., m-cresol, p-cresol, and o-cresol, xylenols, e.g.,
2,5-xylenol, 3,5-xylenol, 3,4-xylenol, and 2,3-xylenol,
alkoxyphenols, e.g., p-methoxyphenol, m-methoxyphenol,
3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol,
p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol,
and p-butoxyphenol, dialkylphenols, e.g.,
2-methyl-4-isopropylphenol, and other hydroxylated aromatics
including m-chlorophenol, p-chlorophenol, o-chlorophenol,
dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and
naphthol. These compounds may be used alone or as a mixture of two
or more thereof. The main monomers for novolak resins should not be
construed as being limited to the above examples.
[0105] Examples of the aldehydes for polycondensation with phenolic
compounds to obtain novolaks include formaldehyde, p-formaldehyde,
acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde,
.alpha.-phenylpropionaldehyde, .beta.-phenylpropionaldehyde,
o-hydroxybenzaldehyde, m-hydroxybenzaldehyde,
p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde,
p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde,
o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde,
p-ethylbenzaldehyde, p-n-butylbenzaldehyde, furfural,
chloroacetaldehyde, and acetals derived from these, such as
chloroacetaldehyde diethyl acetal. Preferred of these is
formaldehyde.
[0106] These aldehydes may be used alone or in combination of two
or more thereof. Examples of the acid catalyst include hydrochloric
acid, sulfuric acid, formic acid, acetic acid, and oxalic acid.
[0107] The weight-average molecular weight of the thus-obtained
novolak resin suitably is from 1'000 to 30'000. If the
weight-average molecular weight thereof is lower than 1'000, the
film reduction at unexposed parts during development is liable to
be large. If the weight-average molecular weight there of exceeds
50'000, the developing rate may be too low. The especially
preferred range of the molecular weight of the novolak resin is
from 2'000 to 20'000. The poly(hydroxystyrene)s and derivatives and
copolymers thereof shown above as alkali-soluble polymers other
than novolak resins each have a weight-average molecular weight of
2'000 or higher, preferably from 4'000 to 200'000, more preferably
from 5'000 to 50'000. From the standpoint of obtaining a polymer
film having improved heat resistance, the weight-average molecular
weight thereof is desirably at least 5'000 or higher.
[0108] Weight-average molecular weight in the context of the
present invention is meant to be the one determined by gel
permeation chromatography and calibrated for with polystyrene
standard.
[0109] In the present invention the alkali-soluble polymers may be
used as a mixture of two or more thereof. In the case where a
mixture of an alkali-soluble polymer and the polymer having groups
which decompose by the action of an acid to enhance solubility in
an alkaline developing solution is used, the addition amount of the
alkali-soluble polymer is preferably up to 80% by weight, more
preferably up to 60% by weight, most preferably up to 40% by
weight, based on the total amount of the photosensitive composition
(excluding the solvent). The amount exceeding 80% by weight is
undesirable because the resist pattern suffers a considerable
decrease in thickness, resulting in poor images and low
resolution.
[0110] In the case where an alkali-soluble polymer is used together
with a dissolution inhibitor, without the polymer having groups
which decompose by the action of an acid, to enhance solubility in
an alkaline developing solution, the amount of the alkali-soluble
polymer is preferably from 40% to 90% by weight, more preferably
from 50 to 85% by weight, most preferably 60 to 80% by weight. If
the amount thereof is smaller than 40% by weight, undesirable
results such as reduced sensitivity are caused. On the other hand,
if it exceeds 90% by weight, the resist pattern suffers a
considerable decrease in film thickness, resulting in poor
resolution and image reproduction.
[0111] The content of the sulfonate derivatives of formula Ia, Ib,
IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa, (component (b)) in
the positive resist according to the present invention is
preferably between 0.01% to 20% by weight, based on the total
amount of all solid components in the photoresist.
[0112] The use of the sulfonate derivatives according to the
invention in chemically amplified systems, which operates on the
principle of the removal of a protecting group from a polymer,
generally produces a positive resist. Positive resists are
preferred over negative resists in many applications, especially
because of their higher resolution. There is, however, also
interest in producing a negative image using the positive resist
mechanism, in order to combine the advantages of the high degree of
resolution of the positive resist with the properties of the
negative resist. This can be achieved by introducing a so-called
image-reversal step as described, for example, in EP 361906. For
this purpose, the image-wise irradiated resist material is before
the developing step treated with, for example, a gaseous base,
thereby image-wise neutralizing the acid which has been produced.
Then, a second irradiation, over the whole area, and thermal
aftertreatment are carried out and the negative image is then
developed in the customary manner.
[0113] Acid-sensitive components that produce a negative resist
characteristically are especially compounds which, when catalysed
by an acid (e.g. the acid formed during irradiation of the
compounds of formulae Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va,
Vb or VIa, are capable of undergoing a crosslinking reaction with
themselves and/or with one or more further components of the
composition. Compounds of this type are, for example, the known
acid-curable resins, such as, for example, acrylic, polyester,
alkyd, melamine, urea, epoxy and phenolic resins or mixtures
thereof. Amino resins, phenolic resins and epoxy resins are very
suitable. Acid-curable resins of this type are generally known and
are described, for example, in "Ullmann's Encyclopadie der
technischen Chemie" [Ullmanns Enceclopedia of Technical Chemistry],
4th Edition, Vol. 15 (1978), p. 613-628. The crosslinker components
should generally be present in a concentration of from 2 to 40,
preferably from 5 to 30, percent by weight, based on the total
solids content of the negative resist composition.
[0114] The invention thus includes, as a special embodiment,
chemically amplified negative, alkali-developable photoresists,
comprising
(a4) an alkali-soluble resin as binder (a5) a component that when
catalysed by an acid undergoes a crosslinking reaction with itself
and/or with the binder, and (b) as photosensitive acid donor an
sulfonate derivative of formula Ia, Ib, IIa, IIb, IIIa, IIIb, IVa,
IVb, Va, Vb or VIa.
[0115] The composition may comprise additionally to the component
(b) other photosensitive acid donors (b1), other photoinitiators
(d) and/or (c) other additives.
[0116] Especially preferred as acid-curable resins (a5) are amino
resins, such as non-etherified or etherified melamine, urea,
guanidine or biuret resins, especially methylated melamine resins
or butylated melamine resins, corresponding glycolurils and urones.
By "resins" in this context, there are to be understood both
customary technical mixtures, which generally also comprise
oligomers, and pure and high purity compounds.
N-hexa(methoxymethyl) melamine and tetramethoxymethyl glucoril and
N,N'-dimethoxymethylurone are the acid-curable resins given the
greatest preference.
[0117] The concentration of the compound of formula Ia, Ib, IIa,
IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa in negative resists in
general is from 0.1 to 30, preferably up to 20, percent by weight,
based on the total solids content of the compositions. From 1 to 15
percent by weight is especially preferred.
[0118] Where appropriate, the negative compositions may comprise a
film-forming polymeric binder (a4). This binder is preferably an
alkali-soluble phenolic resin. Well suited for this purpose are,
for example, novolaks, derived from an aldehyde, for example
acetaldehyde or furfuraldehyde, but especially from formaldehyde,
and a phenol, for example unsubstituted phenol, mono- or
di-chlorosubstituted phenol, such as p-chlorophenol, phenol mono-
or di-substituted by C.sub.1-C.sub.9alkyl, such as o-, m- or
p-cresol, the various xylenols, p-tert-butylphenol, p-nonylphenol,
p-phenylphenol, resorcinol, bis(4-hydroxyphenyl)methane or
2,2-bis(4-hydroxyphenyl)propane. Also suitable are homo- and
co-polymers based on ethylenically unsaturated phenols, for example
homopolymers of vinyl- and 1-propenyl-substituted phenols, such as
p-vinylphenol or p-(1-propenyl)phenol or copolymers of these
phenols with one or more ethylenically unsaturated materials, for
example styrenes. The amount of binder should generally be from 30
to 95 percent by weight or, preferably, from 40 to 80 percent by
weight.
[0119] An especially preferred negative resist composition
comprises from 0.5 to 15 percent by weight of an sulfonate
derivative of formula Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va,
Vb or VIa (component (b)), from 40 to 99 percent by weight of a
phenolic resin as binder (component (a4)), for example one of those
mentioned above, and from 0.5 to 30 percent by weight of a melamine
resin (component (a5)) as crosslinking agent, the percentages
relating to the solids content of the composition. With novolak or
especially with polyvinyl phenol as binder, a negative resist
having especially good properties is obtained. Sulfonate
derivatives can also be used as acid generators, which can be
activated photochemically, for the acid-catalysed crosslinking of,
for example, poly(glycidyl)methacrylates in negative resist
systems. Such crosslinking reactions are described, for example, by
Chae et al. in Pollimo 1993, 17(3), 292.
[0120] The positive and the negative resist compositions may
comprise in addition to the photosensitive acid donor compound of
formula Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa
further photosensitive acid donor compounds (bi), further additives
(c), other photoinitiators (d), and/or sensitizers (e).
[0121] Therefore, subject of the invention also are chemically
amplified resist compositions as described above, in addition to
components (a) and (b), or components (a1), (a2), (a3) and (b), or
components (a4), (a5) and (b) comprising further additives (c),
further photosensitive acid donor compounds (b1), other
photoinitiators (d), and/or sensitizers (e).
[0122] Sulfonate derivatives of the present invention in the
positive and negative resist can also be used together with other,
known photolatent acids (bl), for example, onium salts,
6-nitrobenzylsulfonates, bis-sulfonyl diazomethane compounds, cyano
group-containing oximesulfonate compounds, etc. Examples of known
photolatent acids for chemically amplified resists are described in
U.S. Pat. No. 5,731,364, U.S. Pat. No. 5,800,964, EP 704762, U.S.
Pat. No. 5,468,589, U.S. Pat. No. 5,558,971, U.S. Pat. No.
5,558,976, U.S. Pat. No. 6,004,724, GB 2348644 and particularly in
EP 794457 and EP 795786.
[0123] If a mixture of photolatent acids is used in the resist
compositions according to the invention, the weight ratio of
sulfonate derivatives of formula Ia, Ib, IIa, IIb, IIIa, IIIb, IVa,
IVb, Va, Vb or VIa to the other photolatent acid (b1) in the
mixture is preferably from 1:99 to 99:1.
[0124] Examples of photolatent acids which are suitable to be used
in admixture with the compounds of formula Ia, Ib, IIa, IIb, IIIa,
IIIb, IVa, IVb, Va, Vb or VIa are
(1) onium salt compounds, for example, iodonium salts, sulfonium
salts, phosphonium salts, diazonium salts, pyridinium salts.
Preferred are diphenyliodonium triflate, diphenyliodonium
pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate,
triphenylsulfonium triflate, triphenylsulfonium
hexafluoroantimonate, diphenyliodonium hexafluoroantimonate,
triphenylsulfonium naphthalenesulfonate,
(hydroxyphenyl)benzylmethylsulfonium toluenesulfonate and the like.
Particularly preferred are triphenylsulfonium triflate,
diphenyliodonium hexafluoroantimonate. (2) halogen-containing
compounds haloalkyl group-containing heterocyclic compounds,
haloalkyl group-containing hydrocarbon compounds and the like.
Preferred are (trichloromethyl)-s-triazine derivatives such as
phenyl-bis(trichloromethyl)-s-triazine,
methozyphenyl-bis(trichloromethyl)-s-triazine,
naphthyl-bis-(trichloromethyl)-s-triazine and the like;
1.1-bis(4-chlorophnyl)-2,2,2-trichloroethane; and the like. (3)
sulfone compounds, for example .beta.-ketosulfones,
.beta.-sulfonylsulfones and their .alpha.-diazo derivatives and the
like. Preferred are phenacylphenylsulfone, mesitylphenacylsulfone,
bis(phenylsulfonyl)methane, bis(phenylsulfonyl)diazomethane. (4)
sulfonate compounds, for example alkylsulfonic acid esters,
haloalkylsulfonic acid esters, arylsulfonic acid esters,
iminosulfonates, imidosulfonates and the like. Preferred
imidosulfonate compounds are, for example,
N-(trifluoromethlsulfonyloxy)succinimide,
N-(trifluoromethylsulfonyloxy)phthalimide,
N-(trifluoromethylsulfonyloxy)naphthylimide,
N-(trifluoromethylsulfonyloxy)diphenylmaleimide,
N-(trifluoromethylsulfonyloxy)-bicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximi-
de,
N-(trifluoromethylsulfonyloxy)-7-oxabicyclo-[2,2,1]-hept-5-ene-2,3-dic-
arboximide,
N-(trifluoromethylsulfonyloxy)-7-.alpha.-abicyclo-[2,2,1]-hept-5-ene-2,3--
dicarboximide,
N-(trifluoromethylsulfonyloxy)-bicyclo-[2,2,1]-heptan-5,6-oxy-2,3-dicarbo-
ximide, N-(camphanylsulfonyloxy) succinimide,
N-(camphanylsulfonyloxy)phthalimide,
N-(camphanylsulfonyloxy)naphthylimide,
N-(camphanylsulfonyloxy)diphenylmaleimide,
N-(camphanylsulfonyloxy)bicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide,
N-(camphanylsulfonyloxy)-7-oxabicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximid-
e,
N-(camphanylsulfonyloxy)-7-oxabicyclo-[2,2,1]hept-5-ene-2,3-dicarboximi-
de,
N-(camphanylsulfonyloxy)-bicyclo-[2,2,1]-heptan-5,6-oxy-2,3-dicarboxim-
ide, N-(4-methylphenylsulfonyloxy)succinimide,
N-(4-methylphenylsulfonyloxy)phthalimide,
N-(4-methylphenylsulfonyloxy)naphthylimide,
N-(4-methylphenylsulfonyloxy)naphthylimide,
N-(4-methylphenylsulfonyloxy)diphenylmaleimide,
N-(4-methylphenylsulfonyloxy)-bicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximid-
e,
N-(4-methylphenylsulfonyloxy)-7-oxabicyclo-[2,2,1]-hept-5-ene-2,3-dicar-
boximide,
N-(4-methylphenylsulfonyloxy)-bicyclo-[2,2,1]-heptan-5,6-oxy-2,3-
-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide,
N-(2-trifluoromethylphenylsulfonyloxy)naphthylimide,
N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide,
N-(2-trifluoromethylphenylsulfonyloxy)-bicyclo-[2,2,1]-hept-5-ene-2,3-dic-
arboximide,
N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo-[2,2,1]-hept-5-ene-2,-
3-dicarboximide,
N-(2-trifluoromethylphenylsulfonyloxy)-bicyclo-[2,2,1]-heptan-5,6-oxy-2,3-
-dicarboximide and the like.
[0125] Other suitable sulfonate compounds preferably are, for
example, benzoin tosylate, pyrogallol tristriflate,
pyrogallolomethanesulfonic acid triester,
nitorobenzyl-9,10-diethyoxyanthracene-2-sulfonate,
.alpha.-(4-toluene-sulfonyloxyimino)-benzyl cyanide,
.alpha.-(4-toluene-sulfonyloxyimino)-4-methoxybenzyl cyanide,
.alpha.-(4-toluene-sulfonyloxyimino)-2-thienylmethyl cyanide,
.alpha.-(methanesulfonyloxyimino)-1-cyclohexenylacetonitrile,
.alpha.-(butylsulfonyloxyimino)-1-cyclopentenylacetonitrile,
(4-methylsulfonyloxyimino-cyclohexa-2,5-dienylidene)-phenyl-acetonitrile,
(5-methylsulfonyloxyimino-5H-thiophen-2-ylidene)-phenyl-acetonitrile,
(5-methylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetoni-
trile,
(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)-a-
cetonitrile,
(5-(p-toluenesulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-ac-
etonitrile,
(5-(10-camphorsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-a-
cetonitrile,
(5-methylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-chlorophenyl)-acetoni-
trile,
2,2,2-trifluoro-1-{4-(3-[4-{2,2,2-trifluoro-1-(1-propanesulfonyloxy-
imino)-ethyl}-phenoxy]-propoxy)-phenyl}-ethanone oxime
1-propanesulfonate,
2,2,2-trifluoro-1-{4-(3-[4-{2,2,2-trifluoro-1-(1-p-toluenesulfonyloxyimin-
o)-ethyl}-phenoxy]-propoxy)-phenyl}-ethanone oxime
1-p-toluenesulfonate and the like.
[0126] In the radiation sensitive resin composition of this
invention, particularly preferred sulfonate compounds include
pyrogallolmethanesulfonic acid triester,
N-(trifluoromethylsulfonyloxy)bicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximid-
e, N-(camphanylsulfonyloxy)naphthylimide,
N-(2-trifluoromethylphenylsulfonyloxy)phthalimide,
N-(trifluoromethylsulfonyloxy)-bicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximi-
de, N-(camphanylsulfonyloxy)naphthylimide,
N-(2-trifluoromethylphenylsulfonyloxy)phthalimide and the like.
(5) Quinonediazide compounds, for example
1,2-quinonediazidesulfonic acid ester compounds of polyhydroxy
compounds. Preferred are compounds having a
1,2-quinonediazidesulfonyl group, e.g. a
1,2-benzoquinonediazide-4-sulfonyl group, a
1,2-naphthoquinonediazide-4-sulfonyl group, a
1,2-naphthoquinonediazide-5-sulfonyl group, a
1,2-naphthoquinonediazide-6-sulfonyl group or the like.
Particularly preferred are compounds having a
1,2-naphthoquinonediazide-4-sulfonyl group or a
1,2-naphthoquinonediazide-5-sulfonyl group. In particular suitable
are 1,2-quinonediazidesulfonic acid esters of (poly)hydroxyphenyl
aryl ketones such as 2,3,4-trihydroxybenzophenone,
2,4,6-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone,
2,2',3,4-tetrahydroxybenzophenone,
2,3,4,4'-tetrahydroxybenzophenone,
2,2',4,4'-tetrahydroxybenzophenone
2,2',3,4,-4'-pentahydroxybenzophenone,
2,2'3,2,6'-pentahydroxybenzophenone,
2,3,3',4,4'5'-hexahydroxybenzophenone,
2,3',4,4',5'6-hexahydroxybenzophenone and the like;
1,2-quinonediazidesulfonic acid esters of
bis-[(poly)hydroxyphenyl]alkanes such as
bis(4-hydroxyphenyl)ethane, bis(2,4-dihydroxyphenyl)ethane,
2,2-bis(4-hydroxyphenyl)propane,
2,2-bis(2,4-dihydroxyphenyl)propane,
2,2-bis-(2,3,4-tridroxyphenyl)propane and the like;
1,2-quinonediazidesulfonic acid esters of
(poly)hydroxyphenylalkanes such as 4,4'-dihydroxytriphenylmethane,
4,4'4''-trihydroxytriphenylmethane,
4,4'5,5'-tetramethyl-2,2'2''-trihydroxytriphenylmethane,
2,2,5,5'-tetramethyl-4,4',4''-trihydroxytriphenylmethane,
1,1,1-tris(4-hydroxyphenyl)ethane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
1,1-bis(4-hydroxyphenyl)-1-(4-[1-(hydroxyphenyl)-1-methylethyl]phenyl)eth-
ane and the like; 1,2-quinonediazidesulfonic acid esters of
(poly)hydroxyphenylflavans such as
2,4,4-trimethyl-2',4',7-trihydroxy-2-phenylflavan,
2,4,4-trimethyl-2',4',5',6,7-pentahydroxy-2-phenylflavan and the
like.
[0127] The positive and negative photoresist composition of the
present invention may optionally contain one or more additives (c)
customarily used in photoresists in the customary amounts known to
a person skilled in the art, for example, dyes, pigments,
plasticizers, surfactants, flow improvers, wetting agents, adhesion
promoters, thixotropic agents, colourants, fillers, solubility
accelerators, acid-amplifier, photosensitizers and organic basic
compounds.
[0128] Further examples for organic basic compounds which can be
used in the resist composition of the present invention are
compounds which are stronger bases than phenol, in particular,
nitrogen-containing basic compounds. These compounds may be ionic,
like, for example, tetraalkylammonium salts or non-ionic. Preferred
organic basic compounds are nitrogen-containing basic compounds
having, per molecule, two or more nitrogen atoms having different
chemical environments. Especially preferred are compounds
containing both at least one substituted or unsubstituted amino
group and at least one nitrogen-containing ring structure, and
compounds having at least one alkylamino group. Examples of such
preferred compounds include guanidine, aminopyridine, amino
alkylpyridines, aminopyrrolidine, indazole, imidazole, pyrazole,
pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine,
aminomorpholine, and aminoalkylmorpholines. Suitable are both, the
unsubstituted compounds or substituted derivatives thereof.
Preferred substituents include amino, aminoalkyl groups, alkylamino
groups, aminoaryl groups, arylamino groups, alkyl groups alkoxy
groups, acyl groups acyloxy groups aryl groups, aryloxy groups,
nitro, hydroxy, and cyano. Specific examples of especially
preferred organic basic compounds include guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine,
2-aminopyridine, 3-aminopyridine, 4-aminopyridine,
2-dimethylaminopyridine, 4-dimethylaminopyridine,
2-diethylaminopyridine, 2-(aminomethyl)pyridine,
2-amino-3-methylpyridine, 2-amino-4-methylpyridine,
2-amino-5-methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine,
piperazine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)piperidine,
4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine,
2-imimopiperidine, 1-(2-aminoethyl)pyrrolidine, pyrazole,
3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole,
pyrazine, 2-(aminomethyl)-5-methylpyrazine, pyrimidine,
2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline,
3-pyrazoline, N-aminomorpholine, and
N-(2-aminoethyl)morpholine.
Other examples of suitable organic basic compounds are described in
DE 4408318, U.S. Pat. No. 5,609,989, U.S. Pat. No. 5,556,734, EP
762207, DE 4306069, EP 611998, EP 813113, EP 611998, and U.S. Pat.
No. 5,498,506. However, the organic basic compounds suitable in the
present invention are not limited to these examples.
[0129] The nitrogen-containing basic compounds may be used alone or
in combination of two or more thereof. The added amount of the
nitrogen-containing basic compounds is usually from 0.001 to 10
parts by weight, preferably from 0.01 to 5 parts by weight, per 100
parts by weight of the photosensitive resin composition (excluding
the solvent). If the amount thereof is smaller than 0.001 part by
weight, the effects of the present invention cannot be obtained. On
the other hand, if it exceeds 10 parts by weight, reduced
sensitivity and impaired developability at unexposed parts are
liable to be caused.
[0130] The composition can further contain a basic organic compound
which decomposes under actinic radiation ("suicide base") such as
for example described in EP 710885, U.S. Pat. No. 5,663,035, U.S.
Pat. No. 5,595,855, U.S. Pat. No. 5,525,453, and EP 611998.
[0131] Examples of dyes (c) suitable for the compositions of the
present invention are oil-soluble dyes and basic dyes, e.g. Oil
Yellow #101, Oil Yellow #103, Oil Pink #312, Oil Green BG, Oil Blue
BOS, Oil Blue #603, Oil Black BY, Oil Black BS, Oil Black T-505
(all manufactured by Orient Chemical Industries Ltd., Japan),
crystal violet (CI42555), methyl violet (CI42535), rhodamine B
(CI45170B), malachite green (CI42000), and methylene blue
(CI52015). Spectral sensitizers (e) may be further added to
sensitize the photo latent acid to exhibit absorption in a region
of longer wavelengths than far ultaviolet, whereby the
photosensitive composition of the present invention can, for
example, be rendered sensitive to an i-line or g-line radiation.
Examples of suitable spectral sensitizers include benzophenones,
p,p'-tetra-methyldiaminobenzophenone,
p,p'-tetraethylethylaminobenzophenone, thioxanthone,
2-chlorothioxanthone, anthrone, pyrene, perylene, phenothiazine,
benzil, acridine orange, benzo-flavin, cetoflavin T,
9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene,
2-nitrofluorene, 5-nitroacenaphthene, benzoquinone,
2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline,
N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone,
2-ethylanthraquinone, 2-tert-butylanthraquinone,
1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone,
dibenzalacetone, 1,2-naphthoquinone, 3-acylcoumarin derivatives,
3,3'-carbonyl-bis(5,7-dimethoxycarbonylcoumarin),
3-(aroylmethylene) thiazolines, eosin, rhodamine, erythrosine, and
coronene. However, the suitable spectral sensitizers are not
limited to these examples.
[0132] These spectral sensitizers can be used also as light
absorbers for absorbing the far ultraviolet emitted by a light
source. In this case, the light absorber reduces light reflection
from the substrate and lessens the influence of multiple reflection
within the resist film, thereby diminishing the effect of standing
waves.
[0133] Further suitable additives (c) are "acid-amplifiers",
compounds that accelerate the acid formation or enhance the acid
concentration. Such compounds may also be used in combination with
the sulfonate derivatives of the formulae Ia, Ib, IIa, IIb, IIIa,
IIIb, IVa, IVb, Va, Vb or VIa according to the invention in
positive or negative resists, or in imaging systems as well as in
all coating applications. Such acid amplifiers are described e.g.
in Arimitsu, K. et al. J. Photopolym. Sci. Technol. 1995, 8, pp 43;
Kudo, K. et al. J. Photopolym. Sci. Technol. 1995, 8, pp 45;
Ichimura, K. et al. Chem: Letters 1995, pp 551.
[0134] Usually, for the application to a substrate of the
photosensitive composition of the present invention, the
composition is dissolved in an appropriate solvent. Preferred
examples of these solvents include ethylene dichloride,
cyclohexanone, cyclopentanone, 2-heptanone, .gamma.-butyrolactone,
methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene
glycol monoethyl ether, 2-methoxyethyl acetate, 2-ethoxyethyl
acetate, 2-ethoxyethanol, diethyl glycol dimethyl ether, ethylene
glycol monoethyl ether acetate, propylene glycol monomethyl ether,
propylene glycol monomethyl ether acetate, toluene, ethyl acetate,
methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl
ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate,
N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and
tetrahydrofuran. These solvents may be used alone or as mixtures.
Preferred examples of the solvents are esters, such as
2-methoxyethyl acetate, ethylene glycolmonoethyl ether acetate,
propylene glycol monomethyl ether acetate, methyl
methoxypropionate, ethyl ethoxypropionate, and ethyl lactate. Use
of such solvents is advantageous because the sulfonate derivatives
represented by formulae Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va,
Vb or VIa according to the pre-sent invention have good
compatibility therewith and better solubility therein.
[0135] A surfactant can be added to the solvent. Examples of
suitable surfactants include nonionic surfactants, such as
polyoxyethylene alkyl ethers, e.g. polyoxyethylene lauryl ether,
polyoxyethylene stearyl ether, polyoxyethylene acetyl ether, and
polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers, e.g.
polyoxyethylene, octylphenol ether and polyoxyethylene non-ylphenol
ether; polyoxyethylene/polyoxypropylene block copolymers,
sorbitan/fatty acid esters, e.g. sorbitan monolaurate, sorbitan
monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan
trioleate; fluorochemical surfactants such as F-top EF301, EF303,
and EF352 (manufactured by New Akita Chemical Company, Japan).
Megafac F171 and F17.3 (manufactured by Dainippon Ink &
Chemicals, Inc, Japan), Fluorad FC 430 and FC431 (manufactured by
Sumitomo 3M Ltd., Japan), Asahi Guard AG710 and Surflon S-382,
SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi
Grass Col, Ltd., Japan); organosiloxane polymer KP341 (manufactured
by Shin-Etsu Chemical Co., Ltd., Japan); and acrylic or methacrylic
(co)polymers Poly-flow Now.75 and N0.95 (manufactured by Kyoeisha
Chemical Co., Ltd., Japan). The added amount of the surfactant
usually is 2 parts by weight or lower, desirably 0.5 part by weight
or lower, per 100 parts by weight of the solid components of the
composition of the present invention. The surfactants may be added
alone or in combination of two or more thereof.
[0136] The solution is uniformly applied to a substrate by means of
known coating methods, for example by spin-coating, immersion,
knife coating, curtain pouring techniques, brush application,
spraying and roller coating. It is also possible to apply the
photosensitive layer to a temporary, flexible support and then to
coat the final substrate by coating transfer (laminating).
[0137] The amount applied (coating thickness) and the nature of the
substrate (coating substrate) are dependent on the desired field of
application. The range of coating thicknesses can in principle
include values from approximately 0.01 .mu.m to more than 100
.mu.m.
[0138] After the coating operation generally the solvent is removed
by heating, resulting in a layer of the photoresist on the
substrate. The drying temperature must of course be lower than the
temperature at which certain components of the resist might react
or decompose. In general, drying temperatures are in the range from
60 to 160.degree. C. The resist coating is then irradiated
image-wise. The expression "image-wise irradiation" includes
irradiation in a predetermined pattern using actinic radiation,
i.e. both irradiation through a mask containing a predetermined
pattern, for example a transparency, a chrome mask or a reticle,
and irradiation using a laser beam or electron beam that writes
directly onto the resist surface, for example under the control of
a computer, and thus produces an image. Another way to produce a
pattern is by interference of two beams or images as used for
example in holographic applications. It is also possible to use
masks made of liquid crystals that can be addressed pixel by pixel
to generate digital images, as is, for example described by A.
Bertsch; J. Y. Jezequel; J. C. Andre in Journal of Photochemistry
and Photobiology A: Chemistry 1997, 107 pp. 275-281 and by K. P.
Nicolay in Offset Printing 1997, 6, pp. 34-37.
[0139] After the irradiation and, if necessary, thermal treatment,
the irradiated sites (in the case of positive resists) or the
non-irradiated sites (in the case of negative resists) of the
composition are removed in a manner known per se using a
developer.
[0140] In order to accelerate the catalytic reaction and hence the
development of a sufficient difference in solubility between the
irradiated and unirradiated sections of the resist coating in the
developer, the coating is preferably heated before being developed.
The heating can also be carried out or begun during the
irradiation. Temperatures of from 60 to 160.degree. C. are
preferably used. The period of time depends on the heating method
and, if necessary, the optimum period can be determined easily by a
person skilled in the art by means of a few routine experiments. It
is generally from a few seconds to several minutes. For example, a
period of from 10 to 300 seconds is very suitable when a hotplate
is used and from 1 to 30 minutes when a convection oven is used. It
is important for the latent acid donors according to the invention
in the unirradiated sites on the resist to be stable under those
processing conditions.
[0141] The coating is then developed, the portions of the coating
that, after irradiation, are more soluble in the developer being
removed. If necessary, slight agitation of the workpiece, gentle
brushing of the coating in the developer bath or spray developing
can accelerate that process step. The aqueous-alkaline developers
customary in resist technology may, for example, be used for the
development. Such developers comprise, for example, sodium or
potassium hydroxide, the corresponding carbonates, hydrogen
carbonates, silicates or metasilicates, but preferably metal-free
bases, such as ammonia or amines, for example ethylamine,
n-propylamine, diethylamine, di-n-propylamine, triethylamine,
methyl diethylamine, alkanolamines, for example dimethyl
ethanolamine, triethanolamine, quaternary ammonium hydroxides, for
example tetramethylammonium hydroxide or tetraethylammonium
hydroxide. The developer solutions are generally up to 0.5 N, but
are usually diluted in suitable manner before use. For example
solutions having a normality of approximately 0.1-0.3 are well
suited. The choice of developer depends on the nature of the
photocurable surface coating, especially on the nature of the
binder used or of the resulting photolysis products. The aqueous
developer solutions may, if necessary, also comprise relatively
small amounts of wetting agents and/or organic solvents. Typical
organic solvents that can be added to the developer fluids are, for
example, cyclohexanone, 2-ethoxyethanol, toluene, acetone,
isopropanol and also mixtures of two or more of these solvents. A
typical aqueous/organic developer system is based on
Butylcellosolve.RTM./water.
[0142] Subject of the invention also is a process for the
preparation of a photoresist by [0143] (1) applying to a substrate
a composition as described above; [0144] (2) post apply baking the
composition at temperatures between 60.degree. C. and 160.degree.
C.; [0145] (3) image-wise irradiating with light of wavelengths
between 150 nm and 1500 nm; [0146] (4) optionally post exposure
baking the composition at temperatures between 60.degree. C. and
160.degree. C.; and [0147] (5) developing with a solvent or with an
aqueous alkaline developer.
[0148] Preferred is a process, wherein the image-wise irradiation
is carried out with monochromatic or polychromatic radiation in the
wavelength range from 150 to 450 nm, in particular in the range
from 190 to 260 nm.
[0149] The photoresist compositions can be used on all substrates
and with all exposure techniques known to the person skilled in the
art. For example, semiconductor substrates can be used, such as
silicon, gallium arsenide, germanium, indium antimonide;
furthermore substrate covered by oxide or nitride layers, such as
silicon dioxide, silicon nitride, titanium nitride, siloxanes, as
well as metal substrates and metal coated substrates with metals
such as aluminium, copper, tungsten, etc. The substrate can also be
coated with polymeric materials, for example with organic
antireflective coatings, insulation layers and dielectric coatings
from polymeric materials prior to coating with the photoresist.
[0150] The photoresist layer can be exposed by all common
techniques, such as direct writing, i.e. with a laser beam or
projection lithography in stepp- and repeat mode or scanning mode,
or by contact printing through a mask.
[0151] In case of projection lithography a wide range of optical
conditions can be used such as coherent, partial coherent or
incoherent irradiation. This includes off-axis illumination
techniques, for example annular illumination and quadrupol
illumination where the radiation is allowed to pass only certain
regions of the lens, excluding the lens center.
[0152] The mask used to replicate the pattern can be a hard mask or
a flexible mask. The mask can include transparent, semitransparent
and opaque patterns. The pattern size can include also patterns
which are at or below the resolution limit of the projection optics
and placed on the mask in a certain way in order to modify the
aerial image, intensity and phase modulation of the irradiation
after having passed the mask. This includes phase shift masks and
half-tone phase shift masks.
[0153] The patterning process of the photoresist composition can be
used to generate patterns of any desired geometry and shape, for
example dense and isolated lines, contact holes, trenches, dots,
etc.
[0154] The photoresists according to the invention have excellent
lithographic properties, in particular a high sensitivity, and high
resist transparency for the imaging radiation.
[0155] Possible areas of use of the composition according to the
invention are as follows: use as photoresists for electronics, such
as etching resists, ion-implantation resist, electroplating resists
or solder resists, the manufacture of integrated circuits or thin
film transistor-resist (TFT); the manufacture of printing plates,
such as offset printing plates or screen printing stencils, use in
the etching of mouldings or in stereolithography or holography
techniques. The coating substrates and processing conditions vary
accordingly.
[0156] The compositions according to the invention are also
outstandingly suitable as coating compositions for substrates of
all types, including wood, textiles, paper, ceramics, glass,
plastics, such as polyesters, polyethylene terephthalate,
polyolefins or cellulose acetate, especially in the form of films,
but especially for coating metals, such as Ni, Fe, Zn, Mg, Co or
especially Cu and Al, and also Si, silicon oxides or nitrides, to
which an image is to be applied by means of image-wise
irradiation.
[0157] The invention relates also to the use of compounds of
formula Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa as
photolatent acid donors in compositions that can be crosslinked
under the action of an acid and/or as dissolution enhancers in
compositions wherein the solubility is increased under the action
of an acid.
[0158] Subject of the invention further is a process of
crosslinking compounds that can be crosslinked under the action of
an acid, which method comprises adding a compound of formula I
and/or II to the above-mentioned compounds and irradiating
imagewise or over the whole area with light having a wavelength of
150-1500 nm.
[0159] The invention relates also to the use of compounds of
formulae Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa as
photosensitive acid donors in the preparation of surface coatings,
printing inks, printing plates, dental compositions, colour
filters, resists or image-recording materials, or image-recording
materials for recording holographic images, as well as to a process
for the preparation of surface coatings, printing inks, printing
plates, dental compositions, colour filters, resists,
image-recording materials, or image-recording materials for
recording holographic images.
[0160] Subject of the invention is also the use of compounds of
formulae Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa as
photosensitive acid donors in the preparation of colour filters or
chemically amplified resist materials; as well as to a process for
the preparation of colour filters or chemically amplified resist
materials.
[0161] As already mentioned above, in photocrosslinkable
compositions, sulfonate derivatives act as latent curing catalysts:
when irradiated with light they release acid which catalyses the
crosslinking reaction. In addition, the acid released by the
radiation can, for example, catalyse the removal of suitable
acid-sensitive protecting groups from a polymer structure, or the
cleavage of polymers containing acid-sensitive groups in the
polymer backbone. Other applications are, for example,
colour-change systems based on a change in the pH or in the
solubility of, for example, a pigment protected by acid-sensitive
protecting groups. Sulfonate derivatives according to the present
invention can also be used to produce so-called "print-out" images
when the compound is used together with a colourant that changes
colour when the pH changes, as described e.g. in JP Hei 4 328552-A
or in U.S. Pat. No. 5,237,059. Such color-change systems can be
used according to EP 199672 also to monitor goods that are
sensitive to heat or radiation.
[0162] In addition to a colour change, it is possible during the
acid-catalysed deprotection of soluble pigment molecules (as
described e.g. in EP 648770, EP 648817 and EP 742255) for the
pigment crystals to be precipitated; this can be used in the
production of colour filters as described e.g. in EP 654711 or
print out images and indicator applications, when the colour of the
latent pigment precursor differs from that of the precipitated
pigment crystal.
[0163] Compositions using pH sensitive dyes or latent pigments in
combination with sulfonate derivatives can be used as indicators
for electromagnetic radiation, such as gamma radiation, electron
beams, UV- or visible light, or simple throw away dosimeters.
Especially for light, that is invisible to the human eye, like UV-
or IR-light, such dosimeters are of interest.
[0164] Finally, sulfonate derivatives that are sparingly soluble in
an aqueous-alkaline developer can be rendered soluble in the
developer by means of light-induced conversion into the free acid,
with the result that they can be used as solubility enhancers in
combination with suitable film-forming resins.
[0165] Resins which can be crosslinked by acid catalysis and
accordingly by the photolatent acids of formula Ia, Ib, IIa, IIb,
IIIa, IIIb, IVa, IVb, Va, Vb or VIa according to the invention,
are, for example, mixtures of polyfunctional alcohols or
hydroxy-group-containing acrylic and polyester resins, or partially
hydrolysed polyvinylacetals or polyvinyl alcohols with
polyfunctional acetal derivatives. Under certain conditions, for
example the acid-catalysed self-condensation of
acetal-functionalised resins is also possible.
[0166] Suitable acid-curable resins in general are all resins whose
curing can be accelerated by acid catalysts, such as aminoplasts or
phenolic resole resins. These resins are for example melamine,
urea, epoxy, phenolic, acrylic, polyester and alkyd resins, but
especially mixtures of acrylic, polyester or alkyd resins with a
melamine resin. Also included are modified surface-coating resins,
such as acrylic-modified polyester and alkyd resins. Examples of
individual types of resins that are covered by the expression
acrylic, polyester and alkyd resins are described, for example, in
Wagner, Sarx, Lackkunstharze (Munich, 1971), pp. 86-123 and pp.
229-238, or in Ullmann, Encyclopadie der techn. Chemie, 4th Ed.,
Vol. 15 (1978), pp. 613-628, or Ullmann's Encyclopedia of
Industrial Chemistry, Verlag Chemie, 1991, Vol. 18, p. 360 ff.,
Vol. A19, p. 371 ff.
[0167] In coating applications the surface coating preferably
comprises an amino resin. Examples thereof are etherified or
non-etherified melamine, urea, guanidine or biuret resins. Acid
catalysis is especially important in the curing of surface coatings
comprising etherified amino resins, such as methylated or butylated
melamine resins (N-methoxymethyl- or N-butoxymethyl-melamine) or
methylated/butylated glycolurils. Examples of other resin
compositions are mixtures of polyfunctional alcohols or
hydroxy-group-containing acrylic and polyester resins, or partially
hydrolysed polyvinyl acetate or polyvinyl alcohol with
polyfunctional dihydropropanyl derivatives, such as derivatives of
3,4-dihydro-2H-pyran-2-carboxylic acid. Polysiloxanes can also be
crosslinked using acid catalysis. These siloxane group-containing
resins can, for example, either undergo self-condensation by means
of acid-catalysed hydrolysis or be crosslinked with a second
component of the resin, such as a polyfunctional alcohol, a
hydroxy-group-containing acrylic or polyester resin, a partially
hydrolysed polyvinyl acetal or a polyvinyl alcohol. This type of
polycondensation of polysiloxanes is described, for example, in J.
J. Lebrun, H. Pode, Comprehensive Polymer Science, Vol. 5, p. 593,
Pergamon Press, Oxford, 1989. Other cationically polymerisable
materials that are suitable for the preparation of surface coatings
are ethylenically unsaturated compounds polymerisable by a cationic
mechanism, such as vinyl ethers, for example methyl vinyl ether,
isobutyl vinyl ether, trimethylolpropane trivinyl ether, ethylene
glycol divinyl ether; cyclic vinyl ethers, for example
3,4-dihydro-2-formyl-2H-pyran (dimeric acrolein) or the
3,4-dihydro-2H-pyran-2-carboxylic acid ester of
2-hydroxymethyl-3,4-dihydro-2H-pyran; vinyl esters, such as vinyl
acetate and vinyl stearate, mono- and di-olefins, such as
.alpha.-methylstyrene, N-vinylpyrrolidone or N-vinylcarbazole.
[0168] For certain purposes, resin mixtures having monomeric or
oligomeric constituents containing polymerisable unsaturated groups
are used. Such surface coatings can also be cured using compounds
of formula Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa.
In that process, radical polymerisation initiators or
photoinitiators can additionally be used. The former initiate
polymerisation of the unsaturated groups during heat treatment, the
latter during UV irradiation.
[0169] The invention also relates to a composition comprising
(a) a compound which cures upon the action of an acid or a compound
whose solubility is increased upon the action of an acid; and (b)
as photosensitive acid donor, at least one compound of the formula
Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa as described
above.
[0170] The compounds of formulae Ia, Ib, IIa, IIb, IIIa, IIIb, IVa,
IVb, Va, Vb or VIa respectively, are generally added to the
compositions in an amount from 0.1 to 30% by weight, for example
from 0.5 to 10% by weight, especially from 1 to 5% by weight.
[0171] According to the invention, the compounds of formula Ia, Ib,
IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa can be used together
with further photosensitive acid donor compounds (bl), further
photoinitiators (d), sensitisers (e) and/or additives (c).
[0172] Suitable photosensitive acid donor compounds (bl),
sensitizers (e) and additives (c) are described above.
[0173] Examples of additional photoinitiators (d) are radical
photoinitiators, such as those from the class of the benzophenones,
acetophenone derivatives, such as .alpha.-hydroxycycloalkylphenyl
ketone, dialkoxyacetophenone, .alpha.-hydroxy- or
.alpha.-amino-acetophenone, 4-aroyl-1,3-dioxolans, benzoin alkyl
ethers and benzil ketals, monoacylphosphine oxides,
bisacylphosphine oxides or titanocenes. Examples of especially
suitable additional photoinitiators are:
1-(4-dodecylbenzoyl)-1-hydroxy-1-methyl-ethane,
1-(4-isopropylbenzoyl)-1-hydroxy-1-methyl-ethane,
1-benzoyl-1-hydroxy-1-methyl-ethane,
1-[4-(2-hydroxyethoxy)-benzoyl]-1-hydroxy-1-methylethane,
1-[4-(acryloyloxyethoxy)-benzoyl]-1-hydroxy-1-methyl-ethane,
diphenyl ketone, phenyl-1-hydroxy-cyclohexyl ketone,
(4-morpholinobenzoyl)-1-benzyl-1-dimethylamino-propane,
1-(3,4-dimethoxyphenyl)-2-benzyl-2-dimethylamino-butan-1-one,
(4-methylthiobenzoyl)-1-methyl-1-morpholino-ethane, benzil dimethyl
ketal,
bis(cyclopentadienyl)-bis(2,6-difluoro-3-pyrryl-phenyl)titanium,
trimethylbenzoyldiphenylphosphine oxide,
bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl)-phosphine
oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dipentyloxyphenyl-phosphine
oxide or bis(2,4,6-trimethylbenzoyl)phenyl-phosphine oxide. Further
suitable additional photoinitiators are to be found in U.S. Pat.
No. 4,950,581, column 20, line 35 to column 21, line 35. Other
examples are trihalomethyltriazine derivatives or
hexaarylbisimidazolyl compounds. Further examples for additional
photoinitiators are borate compounds, as for example described in
U.S. Pat. No. 4,772,530, EP 775706, GB 2307474, GB 2307473 and GB
2304472. The borate compounds preferably are used in combination
with electron acceptor compounds, such as, for example dye cations,
or thioxanthone derivatives.
[0174] Further examples of additional photoinitiators are peroxide
compounds, e.g. benzoyl peroxide (other suitable peroxides are
described in U.S. Pat. No. 4,950,581, col. 19, I. 17-25) or
cationic photoinitiators, such as aromatic sulfonium or iodonium
salts, such as those to be found in U.S. Pat. No. 4,950,581, col.
18, I. 60 to col. 19, I. 10, or cyclopentadienyl-arene-iron(II)
complex salts, for example
(.eta..sup.6-isopropylbenzene)(.eta..sup.5-cyclopentadienyl)-iron(II)
hexafluorophosphate.
[0175] The surface coatings may be solutions or dispersions of the
surface-coating resin in an organic solvent or in water, but they
may also be solventless. Of special interest are surface coatings
having a low solvent content, so-called "high solids surface
coatings", and powder coating compositions. The surface coatings
may be clear lacquers, as used, for example, in the automobile
industry as finishing lacquers for multilayer coatings. They may
also comprise pigments and/or fillers, which may be inorganic or
organic compounds, and metal powders for metal effect finishes.
[0176] The surface coatings may also comprise relatively small
amounts of special additives customary in surface-coating
technology, for example flow improvers, thixotropic agents,
leveling agents, antifoaming agents, wetting agents, adhesion
promoters, light stabilisers, antioxidants, or sensitisers.
[0177] UV absorbers, such as those of the
hydroxyphenyl-benzotriazole, hydroxyphenyl-benzophenone, oxalic
acid amide or hydroxyphenyl-s-triazine type may be added to the
compositions according to the invention as light stabilisers.
Individual compounds or mixtures of those compounds can be used
with or without the addition of sterically hindered amines
(HALS).
[0178] Examples of such UV absorbers and light stabilisers are
1. 2-(2'-Hydroxyihenyl)-benzotriazoles, such as
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)-benzotriazole,
2-(3',5'-di-t-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole,
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole,
2-(2'-hydroxy-4'-octyloxyphenyl)-benzotriazole,
2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)-benzotriazole,
2-(3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazole,
mixture of
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro--
benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethyl-hexyloxy)-carbonylethyl]-2'-hydroxyphenyl-
)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-b-
enzotriazole,
2(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-benzotriazo-
le,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-benzot-
riazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy-
phenyl)-benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)-benzotriazole and
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenyl-benzotr-
iazole,
2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-y-
l-phenol]; transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxy-phenyl]-benzotria-
zole with polyethylene glycol 300;
[R--CH.sub.2CH.sub.2--COO(CH.sub.2).sub.3].sub.2-- wherein
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl. 2.
2-Hydroxybenzophenones, such as the 4-hydroxy, 4-methoxy,
4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy or 2'-hydroxy-4,4'-dimethoxy derivative. 3.
Esters of unsubstituted or substituted benzoic acids, such as
4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl
salicylate, dibenzoylresorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol,
3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl
ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester,
3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester,
3,5-di-tert-butyl-4-hydroxybenzoic acid
2-methyl-4,6-di-tert-butylphenyl ester. 4. Acrylates, such as
a-cyano-b,b-diphenylacrylic acid ethyl ester or isooctyl ester,
a-carbomethoxy-cinnamic acid methyl ester,
a-cyano-b-methyl-p-methoxy-cinnamic acid methyl ester or butyl
ester, a-carbomethoxy-p-methoxy-cinnamic acid methyl ester,
N-(b-carbomethoxy-b-cyanovinyl)-2-methyl-indoline. 5. Sterically
hindered amines, such as
bis(2,2,6,6-tetramethyl-piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-piperidyl)succinate,
bis(1,2,2,6,6-pentamethylpiperidyl)sebacate,
n-butyl-3,5-ditert-butyl-4-hydroxybenzyl-malonic acid
bis(1,2,2,6,6-pentamethylpiperidyl) ester, condensation product of
1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic
acid, condensation product of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,
tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetraoate,
1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethyl-piperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl) malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, condensation
product of
N,N'-bis(2,2,6,6-tetra-methyl-4-piperidyl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of
2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazi-
ne and 1,2-bis(3-aminopropylamino)ethane, condensation product of
2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tria-
zine and 1,2-bis(3-aminopropylamino)ethane,
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione,
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)-pyrrolidine-2,5-dione.
6. Oxalic acid diamides, such as 4,4'-dioctyloxy-oxanilide,
2,2'-diethoxy-oxanilide,
2,2'-di-.alpha.-tyloxy-5,5'-di-tert-butyl-oxanilide,
2,2'-didodecyloxy-5,5'-di-tert-butyl-oxanilide,
2-ethoxy-2'-ethyl-oxanilide,
N,N'-bis(3-dimethylaminopropyl)oxalamide,
2-ethoxy-5-tert-butyl-2'-ethyloxanilide and a mixture thereof with
2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of o- and
p-methoxy- and of o- and p-ethoxy-di-substituted oxanilides. 7.
2-(2-Hydroxyphenyl)-1,3,5-triazines, such as
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-
,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazin-
e,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propyloxy)phenyl]-4,6-bis(2,4-dim-
ethyl-phenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimeth-
ylphenyl)-1,3,5-triazine,
2-[4-dodecyl-/tridecyl-oxy-(2-hydroxypropyl)oxy-2-hydroxy-phenyl]-4,6-bis-
(2,4-dimethylphenyl)-1,3,5-triazine. 8. Phosphites and
phosphonites, such as triphenyl phosphite, diphenyl alkyl
phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite,
trilauryl phosphite, trioctadecyl phosphite,
distearyl-pentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol
diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol
diphosphite, bis(2,6-di-tertbutyl-4-methylphenyl)pentaerythritol
diphosphite, bis-isodecyloxy-pentaerythritol diphosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,
bis-(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite,
tristearyl-sorbitol triphosphite,
tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite,
6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosp-
hocine,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-di-
oxaphosphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methyl
phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl
phosphite.
[0179] Such light stabilisers can also be added, for example, to an
adjacent surface-coating layer from which they gradually diffuse
into the layer of stoving lacquer to be protected. The adjacent
surface-coating layer may be a primer under the stoving lacquer or
a finishing lacquer over the stoving lacquer.
[0180] It is also possible to add to the resin, for example,
photosensitisers which shift or increase the spectral sensitivity
so that the irradiation period can be reduced and/or other light
sources can be used. Examples of photosensitisers are aromatic
ketones or aromatic aldehydes (as described, for example, in U.S.
Pat. No. 4,017,652), 3-acyl-coumarins (as described, for example,
in U.S. Pat. No. 4,366,228, EP 738928, EP 22188), keto-coumarines
(as described e.g. in U.S. Pat. No. 5,534,633, EP 538997, JP
8272095-A), styryl-coumarines (as described e.g. in EP 624580),
3-(aroylmethylene)-thiazolines, thioxanthones, condensed aromatic
compounds, such as perylene, aromatic amines (as described, for
example, in U.S. Pat. No. 4,069,954 or WO 96/41237) or cationic and
basic colourants (as described, for example, in U.S. Pat. No.
4,026,705), for example eosine, rhodanine and erythrosine
colourants, as well as dyes and pigments as described for example
in JP 8320551-A, EP747771, JP7036179-A, EP619520, JP6161109-A,
JP6043641, JP 6035198-A, WO 93/15440, EP 568993, JP 5005005-A, JP
5027432-A, JP 5301910-A, JP 4014083-A, JP 4294148-A, EP 359431, EP
103294, U.S. Pat. No. 4,282,309, EP 39025, EP 5274, EP 727713, EP
726497 or DE 2027467.
[0181] Other customary additives are--depending on the intended
use--optical brighteners, fillers, pigments, colourants, wetting
agents or flow improvers and adhesion promoters.
[0182] For curing thick and pigmented coatings, the addition of
micro glass beads or powdered glass fibres, as described in U.S.
Pat. No. 5,013,768, is suitable.
[0183] Sulfonate derivatives can also be used, for example, in
hybrid systems. These systems are based on formulations that are
fully cured by two different reaction mechanisms. Examples thereof
are systems that comprise components that are capable of undergoing
an acid-catalysed crosslinking reaction or polymerisation reaction,
but that also comprise further components that crosslink by a
second mechanism. Examples of the second mechanism are radical full
cure, oxidative crosslinking or humidity-initiated crosslinking.
The second curing mechanism may be initiated purely thermally, if
necessary with a suitable catalyst, or also by means of light using
a second photoinitiator. Suitable additional photoinitiators are
described above.
[0184] If the composition comprises a radically crosslinkable
component, the curing process, especially of compositions that are
pigmented (for example with titanium dioxide), can also be assisted
by the addition of a component that is radical-forming under
thermal conditions, such as an azo compound, for example 2,
2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), a triazene, a
diazosulfide, a pentazadiene or a peroxy compound, such as, for
example, a hydroperoxide or peroxycarbonate, for example tert-butyl
hydroperoxide, as described, for example, in EP 245639. The
addition of redox initiators, such as cobalt salts, enables the
curing to be assisted by oxidative crosslinking with oxygen from
the air.
[0185] The surface coating can be applied by one of the methods
customary in the art, for example by spraying, painting or
immersion. When suitable surface coatings are used, electrical
application, for example by anodic electrophoretic deposition, is
also possible. After drying, the surface coating film is
irradiated. If necessary, the surface coating film is then fully
cured by means of heat treatment.
[0186] The compounds of formulae Ia, Ib, IIa, IIb, IIIa, IIIb, IVa,
IVb, Va, Vb or VIa can also be used for curing mouldings made from
composites. A composite consists of a self-supporting matrix
material, for example a glass fibre fabric, impregnated with the
photocuring formulation. It is known from EP 592139 that sulfonate
derivatives can be used as acid generators, which can be activated
by light in compositions that are suitable for the surface
treatment and cleaning of glass, aluminium and steel surfaces. The
use of such compounds in organosilane systems results in
compositions that have significantly better storage stability than
those obtained when the free acid is used. The compounds of formula
Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb or VIa are also
suitable for this application.
[0187] The sulfonate derivatives of the present invention can also
be used to shape polymers that undergo an acid induced transition
into a state where they have the required properties using
photolithography. For instance the sulfonate derivatives can be
used to pattern conjugated emissive polymers as described, for
example, in M. L. Renak; C. Bazan; D. Roitman; Advanced materials
1997, 9, 392. Such patterned emissive polymers can be used to
manufacture microscalar patterned Light Emitting Diodes (LED) which
can be used to manufacture displays and data storage media. In a
similar way precursors for polyimides (e.g. polyimid precursors
with acid labile protecting groups that change solubility in the
developer) can be irradiated to form patterned polyimide layers
which can serve as protective coatings, insulating layers and
buffer layers in the production of microchips and printed circuit
boards.
[0188] The formulations of the invention may also be used as
conformal coatings, photoimagable insulating layers and dielectrics
as they are used in sequential build up systems for printed circuit
boards, stress buffer layers in the manufacturing of integrated
circuits.
[0189] It is known that conjugated polymers like, e.g. polyanilines
can be converted from semiconductive to conductive state by means
of proton doping. The sulfonate derivatives of the pre-sent
invention can also be used to imagewise irradiate compositions
comprising such conjugated polymers in order to form conducting
structures (exposed areas) embedded in insulating material (non
exposed areas). These materials can be used as wiring and
connecting parts for the production of electric and electronic
devices.
[0190] Suitable radiation sources for the compositions comprising
compounds of formula Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb
or VIa are radiation sources that emit radiation of a wavelength of
approximately from 150 to 1500, for example from 180 to 1000, or
preferably from 190 to 700 nanometers as well as e-beam radiation
and high-energy electromagnetic radiation such as X-rays. Both,
point sources and planiform projectors (lamp carpets) are suitable.
Examples are: carbon arc lamps, xenon arc lamps, medium pressure,
high pressure and low pressure mercury lamps, optionally doped with
metal halides (metal halide lamps), microwave-excited metal vapour
lamps, excimer lamps, superactinic fluorescent tubes, fluorescent
lamps, argon filament lamps, electronic flash lamps, photographic
flood lights, electron beams and X-ray beams generated by means of
synchrotrons or laser plasma. The distance between the radiation
source and the substrate according to the invention to be
irradiated can vary, for example, from 2 cm to 150 cm, according to
the intended use and the type and/or strength of the radiation
source. Suitable radiaiton sources are especially mercury vapour
lamps, especially medium and high pressure mercury lamps, from the
radiation of which emission lines at other wavelengths can, if
desired, be filtered out. That is especially the case for
relatively short wavelength radiation. It is, however, also
possible to use low energy lamps (for example fluorescent tubes)
that are capable of emitting in the appropriate wavelength range.
An example thereof is the Philips TL03 lamp. Another type of
radiation source that can be used are the light emitting diodes
(LED) that emitt at different wavelengths throughout the whole
spectrum either as small band emitting source or as broad band
(white light) source. Also suitable are laser radiation sources,
for example excimer lasers, such as Kr--F lasers for irradiation at
248 nm, Ar--F lasers at 193 nm, or F.sub.2 laser at 157 nm. Lasers
in the visible range and in the infrared range can also be used.
Especially suitable is radiation of the mercury i, h and g lines at
wavelengths of 365, 405 and 436 nanometers. A suitable laser-beam
source is, for example, the argon-ion laser, which emits radiation
at wavelengths of 454, 458, 466, 472, 478, 488 and 514 nanometers.
Nd-YAG-lasers emitting light at 1064 nm and its second and third
harmonic (532 nm and 355 nm respectively) can also be used. Also
suitable is, for example, a helium/cadmium laser having an emission
at 442 nm or lasers that emit in the UV range. With that type of
irradiation, it is not absolutely essential to use a photomask in
contact with the photopolymeric coating to produce a positive or
negative resist; the controlled laser beam is capable of writing
directly onto the coating. For that purpose the high sensitivity of
the materials according to the invention is very advantageous,
allowing high writing speeds at relatively low intensities. On
irradiation, the sulfonate derivatives in the composition in the
irradiated sections of the surface coating decompose to form the
acids.
[0191] In contrast to customary UV curing with high-intensity
radiation, with the compounds according to the invention activation
is achieved under the action of radiation of relatively low
intensity. Such radiation includes, for example, daylight
(sunlight), and radiation sources equivalent to daylight. Sunlight
differs in spectral composition and intensity from the light of the
artificial radiation sources customarily used in UV curing. The
absorption characteristics of the compounds according to the
invention are as well suitable for exploiting sunlight as a natural
source of radiation for curing. Daylight-equivalent artificial
light sources that can be used to activate the compounds according
to the invention are to be understood as being projectors of low
intensity, such as certain fluorescent lamps, for example the
Philips TL05 special fluorescent lamp or the Philips TL09 special
fluorescent lamp. Lamps having a high daylight content and daylight
itself are especially capable of curing the surface of a
surface-coating layer satisfactorily in a tack-free manner. In that
case expensive curing apparatus is superfluous and the compositions
can be used especially for exterior finishes. Curing with daylight
or daylight-equivalent light sources is an energy-saving method and
prevents emissions of volatile organic components in exterior
applications. In contrast to the conveyor belt method, which is
suitable for flat components, daylight curing can also be used for
exterior finishes on static or fixed articles and structures.
[0192] The surface coating to be cured can be exposed directly to
sunlight or daylight-equivalent light sources. The curing can,
however, also take place behind a transparent layer (e.g. a pane of
glass or a sheet of plastics).
[0193] The examples which follow illustrate the invention in more
detail. Parts and percentages are, as in the remainder of the
description and in the claims, by weight, unless stated otherwise.
Where alkyl radicals having more than three carbon atoms are
referred to without any mention of specific isomers, the n-isomers
are meant in each case.
EXAMPLE 1
Synthesis of 2,2,2-trifluoro-1-p-tolyl-ethanone oxime
2-methoxy-ethanesulfonate
##STR00053##
[0195] In 10 mL of terahydrofurane (THF) is dissolved 1.0 g (5.0
mmol) of 2,2,2-trifluoro-1-p-tolyl-ethanone oxime, which is
prepared according to the description in GB 2348644, and the
solution is cooled in an ice-bath. To the solution are added
successively 2-chloroethane-sulfonyl chloride (0.58 mL, 5.5 mmol)
and triethylamine (1.6 mL, 11.5 mmol), and the reaction solution is
stirred at 0.degree. C. for 1 h. Then, methanol (2.0 mL, 50.0 mmol)
and triethylamine (1.60 mL, 11.5 mmol) are added successively, and
the reaction solution is stirred overnight at 70.degree. C. After
cooling the reaction mixture, it is poured into water. The crude
product is extracted with ethyl acetate twice, washed with water,
dried over MgSO.sub.4 and concentrated. The residue is purified by
column chromatography on silica gel with hexane--ethyl acetate
(19:1 to 3:1) as an eluent to afford the product as colorless oil.
The structure is confirmed by the .sup.1H-NMR spectrum
(CDCl.sub.3). .delta. [ppm]: 2.42 (s, 3H), 3.37 (s, 3H), 3.67 (t,
2H), 3.85 (t, 2H), 7.30 (d, 2H), 7.41 (d, 2H).
EXAMPLE 2
Synthesis of 2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime
2-methoxy-ethanesulfonate
##STR00054##
[0197] According to the same procedure as described in example 1,
the product is obtained from
2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime, which is
prepared according to the description in GB 2348644, as slightly
yellowish oil. The structure is confirmed by the .sup.1H-NMR
spectrum (CDCl.sub.3). .delta. [ppm]: 3.37 (s, 3H), 3.68 (t, 2H),
3.86 (t, 2H), 3.88 (s, 3H), 6.99 (d, 2H), 7.55 (d, 2H).
EXAMPLE 3
Synthesis of 2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime
2-(2-methoxy-ethoxy)-ethanesulfonate
##STR00055##
[0199] According to the same procedure as described in example 1,
the product is obtained as yellow oil by using
2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime with
2-methoxy-ethanol. The structure is confirmed by the .sup.1H-NMR
spectrum (CDCl.sub.3). .delta. [ppm]: 3.34 (s, 3H), 3.51 (t, 2H),
3.64 (t, 2H), 3.72 (t, 2H), 3.87 (s, 3H), 3.97 (t, 2H), 6.99 (d,
2H), 7.55 (d, 2H).
EXAMPLE 4
Synthesis of 2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime
2-{2-(2-ethoxy-ethoxy)-ethoxy}-ethanesulfonate
##STR00056##
[0201] According to the same procedure as described in example 1,
the product is obtained as yellow oil by using
2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime with
2-(2-ethoxy-ethoxy)-ethanol. The structure is confirmed by the
.sup.1H-NMR spectrum (CDCl.sub.3). .delta. [ppm]: 1.20 (t, 3H),
3.48-3.75 (m, 12H), 3.88 (s, 3H), 3.99 (t, 2H), 7.01 (d, 2H), 7.56
(d, 2H).
EXAMPLE 5
Synthesis of 2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime
2-(n-butylthio)-ethanesulfonate
##STR00057##
[0203] In 40 mL of THF are dissolved 4.38 g (20.0 mmol) of
2,2,2-Trifluoro-1-(4-methoxyphenyl)-ethanone oxime and the solution
is cooled in an ice-bath. To the solution are added successively
2-chloroethanesulfonyl chloride (2.3 mL, 22.0 mmol) and
triethylamine (6.4 mL, 46.0 mmol), and the reaction solution is
stirred at 0.degree. C. for 1 h. Then, 1-butanethiol (2.4 mL, 22.0
mmol) and triethylamine (4.2 mL, 30.0 mmol) are added successively,
and the reaction solution is stirred at room temperature for 0.5 h.
After the reaction mixture is poured into water, the crude product
is extracted with ethyl acetate twice, washed with water, dried
over MgSO.sub.4 and concentrated. The residue is purified by column
chromatography on silica gel with hexane--ethyl acetate (10:1 to
5:1) as an eluent to afford the product as yellow oil. The
structure is confirmed by the .sup.1H-NMR spectrum (CDCl.sub.3).
.delta. [ppm]: 0.92 (t, 3H), 1.41 (m, 2H), 1.57 (m, 2H), 2.56 (t,
2H), 2.93 (t, 2H), 3.66 (t, 2H), 3.87 (s, 3H), 7.00 (d, 2H), 7.55
(d, 2H).
EXAMPLE 6
Synthesis of 2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime
2-(3-hydroxypropylthio)-ethanesulfonate
##STR00058##
[0205] According to the same procedure as described in example 5,
the product is obtained as colorless oil by using
3-mercapto-1-propanol. The structure is confirmed by the
.sup.1H-NMR spectrum (CDCl.sub.3). .delta. [ppm]: 1.49 (bs, 1H),
1.85 (m, 2H), 2.70 (t, 2H), 2.96 (t, 2H), 3.68 (t, 2H), 3.75 (m,
2H), 3.87 (s, 3H), 7.00 (d, 2H), 7.55 (d, 2H).
EXAMPLE 7
Synthesis of 2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime
2-(p-hydroxy-phenylthio)-ethanesulfonate
##STR00059##
[0207] According to the same procedure as described in example 5,
the product is obtained as white solid by using 4-mercaptophenol.
The structure is confirmed by the .sup.1H-NMR spectrum
(CDCl.sub.3). .delta. [ppm]: 3.16 (t, 2H), 3.58 (t, 2H), 3.87 (s,
3H), 5.07 (s, 1H), 6.82 (d, 2H), 6.99 (d, 2H), 7.34 (d, 2H), 7.50
(d, 2H). mp. 119-121.degree. C.
EXAMPLE 8
Synthesis of 2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime
2-(p-toluene-sulfonyl)-ethanesulfonate
##STR00060##
[0209] In 40 mL of THF are dissolved 4.38 g (20.0 mmol) of
2,2,2-Trifluoro-1-(4-methoxyphenyl)-ethanone oxime and the solution
is cooled in an ice-bath. To the solution are added successively
2-chloroethanesulfonyl chloride (2.3 mL, 22.0 mmol) and
triethylamine (6.4 mL, 46.0 mmol), and the reaction solution is
stirred at 0.degree. C. for 1 h. Then, p-toluenesulfinic acid
sodium salt (3.56 g, 20.0 mmol) in dimethylformamide (DMF) (80 mL)
is added and the reaction solution is stirred at room temperature
for 0.5 h. After the reaction mixture is poured into water, the
crude product is extracted with ethyl acetate twice, washed with
water, dried over MgSO.sub.4 and concentrated. The residue is
purified by recrystallization from ethanol/toluene to afford the
product as white solid. The structure is confirmed by the
.sup.1H-NMR spectrum (CDCl.sub.3). .delta. [ppm]: 2.49 (s, 3H),
3.53 (t, 2H), 3.77 (t, 2H), 3.88 (s, 3H), 7.00 (d, 2H), 7.42 (d,
2H), 7.50 (d, 2H), 7.80 (d, 2H). mp. 157-158.degree. C.
EXAMPLE 9
Synthesis of 2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime
2-(1,3-dioxo-1,3-dihydro-isoindol-2-yl)-ethanesulfonate
##STR00061##
[0211] According to the same procedure as described in example 8,
the product is obtained as white solid by using phthalimide
potassium salt. The structure is confirmed by the .sup.1H-NMR
spectrum (CDCl.sub.3). .delta. [ppm]: 3.87 (s, 3H), 3.87 (t, 2H),
4.21 (t, 2H), 6.97 (d, 2H), 7.50 (d, 2H), 7.73-7.75 (m, 2H),
7.84-7.86 (m, 2H). mp. 98-107.degree. C.
EXAMPLE 10
Synthesis of
2,2,2-Trifluoro-1-(4-{3-[4-(2,2,2-trifluoro-1-vinylsulfonyloxyimino-ethyl-
)-phenoxy]-propoxy}-phenyl)-ethanone oxime vinylsulfonate
##STR00062##
[0213] In 30 mL of CH.sub.2Cl.sub.2 are dissolved 3.0 g (6.66 mmol)
of
2,2,2-Trifluoro-1-(4-{3-[4-(2,2,2-trifluoro-1-hydroxyimino-ethyl)-phenoxy-
]-propoxy}-phenyl)-ethanone oxime, which is prepared according to
the method described in GB 2348644, and the solution is cooled in
an ice-bath. To the solution are added successively 2,6-lutidine
(3.5 mL, 30.0 mmol) and 2-chloro-ethanesulfonyl chloride (1.55 mL,
14.7 mmol), and the reaction solution is stirred at 0.degree. C.
for 1 h and at room temperature for 2.5 h. Then, it is poured into
1N HCl. The crude product is extracted with CH.sub.2Cl.sub.2,
washed with 1N HCl, dried over MgSO.sub.4 and concentrated. The
residue is purified by recrystallization from methanol to afford
the product as a beige solid. The structure is confirmed by the
.sup.1H-NMR spectrum (CDCl.sub.3). .delta. [ppm]: 2.32 (m, 2H),
4.23 (t, 4H), 6.32 (d, 2H), 6.61 (d, 2H), 6.72 (dd, 2H), 7.00 (d,
4H), 7.50 (d, 4H). mp. 84-88.degree. C.
EXAMPLE 11
Synthesis of 2,2,2-trifluoro-1-p-tolyl-ethanone oxime
vinylsulfonate
##STR00063##
[0215] According to the same procedure as described in example 10,
the product is obtained as yellow oil by using
2,2,2-trifluoro-1-p-tolyl-ethanone oxime. The structure is
confirmed by the .sup.1H-NMR spectrum (CDCl.sub.3). .delta. [ppm]:
2.42 (s, 3H), 6.33 (d, 1H), 6.61 (d, 1H), 6.72 (dd, 1H), 7.30 (d,
2H), 7.39 (d, 2H).
EXAMPLE 12
Synthesis of bis[2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone
oxime] 3,7-dithianonane-1,9-disulfonate
##STR00064##
[0217] According to the same procedure as described in example 5,
the product is obtained as yellowish solid by using
1,3-propanedithiol as educt. The structure is confirmed by the
.sup.1H-NMR spectrum (CDCl.sub.3). .delta. [ppm]: 1.88 (tt, 2H),
2.67 (t, 4H), 2.94 (m, 4H), 3.66 (m, 4H), 3.87 (s, 6H), 7.00 (d,
4H), 7.54 (d, 4H). mp. 46-80.degree. C.
EXAMPLE 13
Synthesis of
5-{2-(methanesulfonyl)-ethanesulfoxy}-imino-5H-thiophen-2-ylidene-o-tolyl-
-acetonitrile
##STR00065##
[0219] A solution of 4.85 g (20.0 mmol) of
5-hydroxyimino-5H-thiophen-2-ylidene-o-tolyl-acetonitrile (prepared
according to U.S. Pat. No. 6,004,724) is treated successively with
triethylamine (6.4 ml, 46.0 mmol) and 2-chloroethanesulfonyl
chloride (2.3 ml, 22.0 mmol) while cooling over an ice-bath. After
stirring for 1 h at 0.degree. C. a solution of 2.04 g (20.0 mmol)
of sodium methanesulfinate (prepared according to the procedure of
L. Field, J. W. McFarland, J. Am. Chem. Soc. 1953, 75, 5582-86) in
methanol (30 ml) is added dropwise to the dark mixture at 0.degree.
C. Stirring is continued for 1 h at room temperature and the
solvent evaporated under reduced pressure. The residue is
redissolved in ethyl acetate (200 ml) and poured into water (100
ml). The aqueous phase is extracted two times with 200 ml of ethyl
acetate and the combined organic phases washed with 200 ml of
brine. After drying over MgSO.sub.4 the organic phase is
concentrated to 150 ml and treated with 1.45 g activated charcoal.
Stirring for 1 h at room temperature, filtration and concentration
provides a dark yellow-green solid (5.87 g). The solid is further
purified by two recrystallizations from 2-propanol, yielding 2.93 g
product as a yellow-green solid. The structure is confirmed by the
.sup.1H-NMR spectrum (CDCl.sub.3). .delta. [ppm]: 2.38 (s, 3H),
3.03 (s, 3H), 3.70-3.81 (m, 2H), 4.03-4.13 (m, 2H), 6.23 (d, 1H),
6.88 (d, 1H), 7.19-7.42 (m, 4H). mp. 144-146.degree. C.
EXAMPLE 14
Synthesis of
5-{2-(p-toluenesulfonyl)-ethanesulfoxy}-imino-5H-thiophen-2-ylidene-o-tol-
yl-acetonitrile
##STR00066##
[0221] The title compound is prepared according to the same
procedure as described in example 12, with p-toluenesulfinic acid
sodium salt (5.00 g, 20.0 mmol). The residue is purified by two
recrystallizations from 2-propanol yielding 4.47 g of the product
as a green-brown solid. The structure is confirmed by the
.sup.1H-NMR spectrum (CDCl.sub.3). .delta. [ppm]: 2.38 (s, 3H),
2.44 (s, 3H), 3.66-3.74 (m, 2H), 3.90-3.99 (m, 2H), 6.20 (d, 1H),
6.84 (d, 1H), 7.18-7.43 (m, 6H), 7.82 (d, 2H). mp. 132-134.degree.
C.
EXAMPLE 15
Synthesis of
N-(ethenesulfonyloxy)-5-norbornene-2,3-dicarboximide
##STR00067##
[0223] A suspension of 5.38 g (30.0 mmol) of
N-hydroxy-5-norbornene-2,3-dicarboximide and CH.sub.2Cl.sub.2 (120
ml) is successively treated with 2-chloroethanesulfonyl chloride
(6.3 ml, 60.0 mmol) at room temperature and triethylamine (12.5 ml,
90.0 mmol) at 0.degree. C. Stirring is continued for 1.5 h at room
temperature and the resulting reaction mixture is treated with 10%
aqueous sodium carbonate solution (100 ml) and ethyl acetate (200
ml). The organic phase is washed with water (100 ml), dried over
Na.sub.2SO.sub.4, and concentrated. The residue is further dried
under vacuum, providing 5.89 g of pure product as light-yellow
solid. The structure is confirmed by the .sup.1H-NMR spectrum
(CDCl.sub.3). .delta. [ppm]: 1.53 (d, 1H), 1.76-1.81 (m, 1H), 3.12
(s, 2H), 3.48 (s, 2H), 6.17 (s, 2H), 6.29 (d, 1H), 6.53 (d, 1H),
6.78 (dd, 1H).
EXAMPLE 16
Synthesis of
N-(2-cyclohexylsulfanyl-ethanesulfonyloxy)-5-norbornene-2,3-dicarboximide
##STR00068##
[0225] A solution of 5.38 g (30.0 mmol) of
N-hydroxy-5-norbornene-2,3-dicarboximide in THF (75 ml) is treated
successively with 2-chloroethanesulfonyl chloride (3.47 ml, 33.0
mmol) and triethylamine (9.6 ml, 69.0 mmol) while cooling over an
ice-bath. After stirring for 1 h at 0.degree. C. triethylamine (6.3
ml, 45.0 mmol) is added first, followed by the addition of
cyclohexanethiol (4.05 ml, 33.0 mmol). The beige suspension is
further stirred for 1 h at room temperature, then poured into water
(140 ml) and extracted two times with ethyl acetate (300 ml). The
combined organic phases are washed with water (300 ml), dried over
MgSO.sub.4, and concentrated. The residue is purified by flash
chromatography on silica gel with hexane and ethyl acetate (7:3) as
eluent, yielding 9.22 g of the product as a white solid. The
structure is confirmed by the .sup.1H-NMR spectrum (CDCl.sub.3).
.delta. [ppm]: 1.21-1.40 (m, 6H), 1.50-1.56 (m, 1H), 1.58-1.67 (m,
1H), 1.74-1.85 (m, 3H), 1.92-2.04 (m, 2H), 2.67-2.79 (m, 1H),
3.03-3.11 (m, 2H), 3.34 (s, 2H), 3.48 (s, 2H), 3.62-3.70 (m, 2H),
6.19 (s, 2H). mp. 96-98.degree. C.
EXAMPLE 17
Synthesis of
N-(2-hexylsulfanyl-ethanesulfonyloxy)-5-norbornene-2,3-dicarboximide
##STR00069##
[0227] The compound is prepared according to the same procedure as
described in example 15, with 1-hexanethiol (9.3 ml, 66.0 mmol) as
starting material. 22.8 g of pure product are obtained as yellow
oil. The structure is confirmed by the .sup.1H-NMR spectrum
(CDCl.sub.3). .delta. [ppm]: 0.90 (t, 3H), 1.22-1.44 (m, 6H),
1.50-1.68 (m, 3H), 1.80 (d, 1H), 2.59 (t, 2H), 3.02-3.09 (m, 2H),
3.32 (s, 2H), 3.48 (s, 2H), 3.63-3.70 (m, 2H), 6.19 (s, 2H).
EXAMPLE 18
Synthesis of
N-(2-di-n-hexylamino-ethanesulfonyloxy)-5-norbornene-2,3-dicarboximide
##STR00070##
[0229] The compound is prepared according to the same procedure as
described in example 15, using di-n-hexylamine (6.12 g, 33.0 mmol)
as a starting material. The residue is purified by flash
chromatography on silica gel with hexane and ethyl acetate (5:2) as
eluent, yielding 9.63 g of the product as orange, viscous oil. The
structure is confirmed by the .sup.1H-NMR spectrum (CDCl.sub.3).
.delta. [ppm]: 0.89 (t, 6H), 1.22-1.35 (m, 12H), 1.36-1.47 (m, 4H),
1.52 (d, 1H), 1.76-1.82 (m, 1H), 2.43 (t, 4H), 3.08-3.14 (m, 2H),
3.31 (m, 2H), 3.48 (m, 2H), 3.54-3.62 (m, 2H), 6.18 (s, 2H).
EXAMPLE 19
Synthesis of
1-[2-(3,5-dioxo-4-aza-tricyclo[5.2.1.0.sup.2,6]dec-8-en-4-yloxysulfonyl)--
ethyl]-pyridinium nonafluorobutane-1-sulfonate
##STR00071##
[0230] 19.1: Synthesis of
N-(2-chloroethanesulfonyloxy)-5-norbornene-2,3-dicarboximide
##STR00072##
[0232] A solution of 12.5 g (70.0 mmol) of
N-hydroxy-5-norbornene-2,3-dicarboximide and pyridine (6.2 ml, 77.0
mmol) in CH.sub.2Cl.sub.2 (105 ml) is treated dropwise with
2-chloroethanesulfonyl chloride (7.36 ml, 70.0 mmol) at 0.degree.
C., according to the procedure of W. C. Groutas, M. A. Stanga, J.
C. Castrisos, E. J. Schatz, M. J. Brubaker J. Pharm. Sci. 1990, 79,
886-88. After stirring overnight at room temperature, the reaction
mixture is diluted with ethyl acetate (280 ml) and then treated
with 5% aqueous HCl (130 ml). The layers are separated and the
aqueous layer is extracted once with ethyl acetate (280 ml). The
combined organic extracts are dried over Na.sub.2SO.sub.4 and
evaporated under reduced pressure, leaving a colorless oil which
solidifies when further dried under vacuum. 15.6 g (73%) of the
product are obtained as a white solid.
19.2: Synthesis of
1-[2-(3,5-dioxo-4-aza-tricyclo[5.2.1.0.sup.2,6]dec-8-en-4-yloxysulfonyl)--
ethyl]-pyridinium chloride
##STR00073##
[0234] A solution of 6.32 g (20.7 mmol) of the compound of example
19.1 in CH.sub.2Cl.sub.2 (100 ml) is treated with pyridine (3.66
ml, 45.5 mmol) and stirred at room temperature overnight. The
precipitated solid is collected and washed immediately with diethyl
ether. Drying under vacuum yields 5.30 g (67%) of the product as a
white solid. The structure is confirmed by the .sup.1H-NMR spectrum
(DMSO-d.sub.6). .delta. [ppm]: 1.53 (q, 2H), 3.29 (s, 2H), 3.35 (s,
2H), 4.60 (t, 2H), 5.23 (t, 2H), 6.06 (s, 2H), 8.19 (t, 2H), 8.64
(t, 1H), 9.18 (d, 2H).
19.3: Synthesis of
1-[2-(3,5-dioxo-4-aza-tricyclo[5.2.1.0.sup.2,6]dec-8-en-4-yloxysulfonyl)--
ethyl]-pyridinium nonafluorobutane-1-sulfonate
[0235] A solution of 4.00 g (10.4 mmol) of the compound of example
19.2 in water (40 ml) is treated dropwise with a solution of
nonafluoro-1-butanesulfonic acid potassium salt (5.27 g, 15.6 mmol)
in water/methanol (40 ml/27 ml). Stirring is continued overnight at
room temperature and the precipitated solid is filtered off and
subsequently washed twice with water. 5.75 g (85%) of the product
is obtained as a white solid. The structure is confirmed by the
.sup.1H-NMR spectrum (acetone-d.sub.6). .delta. [ppm]: 1.67 (dd,
2H), 3.41 (s, 2H), 3.57 (s, 2H), 4.59 (t, 2H), 5.52 (t, 2H), 6.15
(s, 2H), 8.35 (t, 2H), 8.85 (t, 1H), 9.29 (d, 2H). mp.
142-143.degree. C.
EXAMPLE 20
[0236] A chemically amplified positive resist formulation is
prepared by mixing the following components: [0237] 100.00 parts of
a resin binder (a copolymer of 22 mol-% of styrene, 69 mol-% of
p-hydroxy-styrene and 9 mol-% of t-butyl acrylate, having a Mw of
9850; .RTM.Maruzen MARUKA LYNCUR PHS/STY/TBA, provided by Maruzen
Oil Company, Japan) [0238] 0.48 parts of a levelling agent (FC-430,
provided by 3M) [0239] 475.00 parts of propylene glycol methyl
ether acetate (PGMEA) (provided by Tokyo Kasei, Japan) [0240] 4.00
parts of the photoacid generator to be tested
[0241] The resist formulation is spin coated onto a hexamethyl
dimethylsilazane-treated silicone wafer at 3000 rpm for 45 seconds
and softbaked for 90 seconds at 140.degree. C. on a hotplate to
obtain a film thickness of 800 nm. The resist film is then exposed
to deep UV radiation of 254 nm wavelength through a narrow band
interference filter and a multidensity quartz mask using an Ushio's
high pressure mercury lamp, UXM-501 MD, and a mask aligner Canon
PLA-521. The samples then are post exposure baked for 90 seconds at
140.degree. C. on a hotplate and developed. The exposure intensity
is measured with a Unimeter UIT-150 from Ushio. The Dose to Clear
(E.sub.0), which is the dose just sufficient to completely remove
the resist film with 60 seconds immersion development in 1.79%
aqueous tetramethyl ammonium hydroxide developer is determined from
the measured contrast curve. The smaller the required dose the more
sensitive is the resist formulation. The results are collected in
Table 1 and demonstrate that the compositions are suitable for the
preparation of positive photoresists.
TABLE-US-00001 TABLE 1 Compound of example Dose to Clear (E.sub.0)
[mJ/cm.sup.2] 1 0.81 3 3.30 4 1.60 5 1.23 8 1.20 9 1.75 10 2.67 16
4.25 19 2.91
EXAMPLE 21
[0242] The degradation point (Td) of the photolatent acid generator
compound in the presence of the same amount (with respect to the
weight) of poly(4-hydroxystyrene), which has a Mw of 5100 and is
commercially available under the trade name of .RTM.Maruzene MARUKA
LYNCUR PHMC from Maruzene Oil Company of Tokyo, Japan, is
determined by DSC analysis (Differential Scanning Calorimetry). The
higher the values, the more thermostable are the tested photolatent
acid compounds. The results are summarized in the table 2
below.
TABLE-US-00002 TABLE 2 Compound of example Td (.degree. C.) 4 177 5
174 8 195 9 155 10 169 12 181
* * * * *