Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
1999-05-04
2001-01-09
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S558000, C430S556000, C430S557000, C430S551000
Reexamination Certificate
active
06171773
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to a colour photographic print material containing at least one pyrrolo[1,2-b]-1,2,4-triazole as the cyan coupler.
Colour photographic print materials are in particular materials for producing colour reflection prints or display images which most frequently have a positive image. They are thus not recording materials like colour photographic films.
Pyrrolo[1,2-b]-1,2,4-triazoles are cyan couplers known, for example from EP 628 867, which yield very clear cyan dyes having a relatively short-wave absorption band and very high absorbance and thus allow economies of silver halide to be made. The cyan dyes of these couplers additionally exhibit very good stability when stored in darkness.
A disadvantage is that these couplers result in distorted colour reproduction of blue and cyan tones.
The object of the invention is to remedy this disadvantage so that the advantages of these couplers may be exploited.
It has surprisingly now been found that this object may be achieved in a material of the above-stated type having at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler and at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, which material contains in the red-sensitive layer, of which there is at least one, at least one pyrrolo[1,2-b]-1,2,4-triazole cyan coupler of the formula (I)
in which
R
1
means hydrogen or a substituent,
X means a hydrogen atom or a leaving group and
Y means OR
2
or
wherein
R
2
means
or alkyl,
R
3
means alkyl,
R
4
means hydrogen or R
3
,
R
5
, R
6
, R
8
and R
9
mean hydrogen or a substituent,
R
7
means a substituent and
Z means the remaining non-metallic members of a 3- to 8-membered ring, wherein Z may be further substituted, if a two-equivalent yellow coupler is associated with the red-sensitive layer, of which there is at least one.
The yellow coupler is preferably used in the red-sensitive layer, of which there is at least one. The quantity of yellow coupler in the red-sensitive layer is in particular 1 to 10 mol. % of the quantity of the cyan coupler of the formula (I).
The two-equivalent yellow coupler used in the red-sensitive layer preferably has a coupling rate which is no more than five times the coupling rate of the pyrrolotriazole cyan coupler. The coupling rate is determined using a method described in
J. Phot. Sci.
36, 1988, page 14.
Two-equivalent couplers almost always couple substantially faster than cyan couplers. It would have been expected that a cyan layer of the structure according to the invention would exhibit a colour change from the lower to higher densities, with the low densities exhibiting a strong shift towards yellow or green.
Surprisingly, however, this does not occur.
Preferred two-equivalent yellow couplers are acetanilides, in particular pivaloylacetanilides and malonic anilides, the leaving groups of which are attached to the coupler molecule via O or N and which are substituted by chlorine, alkoxy or aryloxy in the ortho position of the anilide portion.
Very particularly preferred two-equivalent yellow couplers are of the formula (III):
in which
R
31
means alkyl, preferably having 1 to 4 C atoms, in particular methyl,
R
32
means alkyl, preferably having 1 to 4 C atoms, in particular methyl,
R
33
means a hydrogen atom or alkyl, preferably having 1 to 4 C atoms, in particular methyl or
R
32
and R
33
together mean the remaining members of a cyclopropyl residue,
R
34
means chlorine or alkoxy,
R
35
means —NHCO—R
37
, —SO
2
NH—R
37
, —NHSO
2
—R
37
, —COOR
37
, Cl, Br or alkoxy
R
36
means a hydrogen or chlorine atom,
R
37
means a substituent, in particular a ballast group and
Q means the remaining members of a substituted imidazole, imidazolidinedione, oxazolidinedione or triazolidinedione ring,
wherein the alkyl groups may be further substituted.
In a preferred embodiment, the red-sensitive layer, of which there is at least one, additionally contains at least one N,N-disubstituted p-aminophenol ether of the formula (II)
in which
R
21
means an alkyl, alkenyl or aryl group,
R
22
and R
23
mutually independently mean a hydrogen atom or an alkyl or alkoxy group having up to 16 C atoms,
R
24
means a hydrogen atom or an alkyl group, in particular a methyl group,
R
25
means a C
1
-C
3
alkylene group and
X
1
means an oxygen atom or a free electron pair,
wherein alkyl groups may be further substituted.
Addition of the compounds of the formula (II) also improves the reproduction of skin tones.
There are various possible arrangements for the combined incorporation of the cyan coupler, yellow coupler and p-aminophenol ether according to the invention in a single layer: the compounds may be present
in a common emulsion in at least one coupler solvent,
in three separate emulsions each optionally having at least one coupler solvent and
in two emulsions, wherein the preferred arrangement is that in which the cyan coupler and the p-aminophenol ether are present together in one emulsion and the yellow coupler in the other emulsion.
Suitable pyrrolo[1,2-b]-1,2,4-triazole cyan couplers of the formula (I) are:
Nr.
R
1
X
Y
I-1
H
I-2
I-3
t-C
4
H
9
I-4
I-5
H
I-6
H
I-7
H
Suitable compounds of the formula (II) are compounds of the following formula:
Nr.
R
21
R
22
R
23
R
24
II-1
—OC
12
H
25
(n)
H
H
H
II-2
—OC
14
H
29
(n)
H
H
H
II-3
—OC
16
H33(n)
H
H
H
II-4
H
H
II-5
H
H
H
II-6
—OC
12
H
25
(n)
CH
3
H
H
II-7
—OC
12
H
25
(n)
OCH
3
H
H
II-8
—OCH
3
—OC
12
H
25
(n)
H
H
II-9
—OC
14
H
29
(n)
H
H
CH
3
II-10
H
H
H
II-11
—OC
3
H
7
(i)
—OC
3
H
7
(i)
—C
3
H
7
(i)
H
The compounds of the formula (II) are in particular used in a quantity of 0.01 to 10 mol./mol. of the cyan coupler of the formula (I), preferably 0.04 to 2 mol./mol. of the cyan coupler.
Up to 25 wt. % of the cyan couplers of the formula (I) may be replaced by other cyan couplers.
Further preferred embodiments of the invention are to be found in the subordinate claims.
Suitable yellow couplers of the formula (III) are
Examples of colour photographic print materials are colour photographic paper, colour reversal photographic paper and semi-transparent display material. A review is given in
Research Disclosure
37038 (1985),
Research Disclosure
38957 (1996) and
Research Disclosure
40145 (1997).
The photographic print materials consist of a support onto which at least one photosensitive silver halide emulsion layer is applied. Thin films and sheets are in particular suitable as supports. A review of support materials and the auxiliary layers applied to the front and reverse sides of which is given in
Research Disclosure
37254, part 1 (1995), page 285 and in
Research Disclosure
38957, part XV (1996), page 627.
The colour photographic print materials conventionally contain at least one red-sensitive, one green-sensitive and one blue-sensitive silver halide emulsion layer, optionally together with interlayers and protective layers.
Depending upon the type of the photographic print material, these layers may be differently arranged. This is demonstrated for the most important products:
Colour photographic paper and colour photographic display material conventionally have on the support, in the stated sequence, one blue-sensitive, yellow-coupling silver halide emulsion layer, one green-sensitive, magenta-coupling silver halide emulsion layer and one red-sensitive, cyan-coupling silver halide emulsion layer; a yellow filter layer is not required.
The number and arrangement of the photosensitive layers may be varied in order to achieve specific results. For example, colour papers may also contain differently sensitised interlayers, by means of which gradation may be influenced.
The substantial constituents of the photographic emulsion layers are binder, silver halide grains and colour couplers.
Details of suitable binders may be found in
Research Disclosure
37254, part 2 (1995), page 2
Bergthaller Peter
Draber Edgar
Hagemann Jorg
Jung J{umlaut over (u)}rgen
Nickel Ulrich
Agfa N.V
Connolly Bove Lodge & Hutz
Letscher Geraldine
LandOfFree
Color photographic print material does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Color photographic print material, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Color photographic print material will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2437884