Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
2001-02-26
2002-04-30
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S631000, C430S635000, C430S636000, C430S505000, C430S955000, C430S957000, C430S552000, C430S553000, C430S554000, C430S555000, C430S557000
Reexamination Certificate
active
06379879
ABSTRACT:
This invention relates to a colour photographic material having at least one spectrally sensitised silver halide emulsion layer, which contains an oil former, together with a coupler which releases a development inhibitor on colour development.
It is known t o perform chromogenic development in the presence of compounds which, on development, release diffusible substances in accordance with the image, which substances perform a certain action, for example are capable of influencing silver halide development. In the event that said action comprises inhibition of further development, such compounds are known as DIR (=Development Inhibitor Releasing) compounds. DIR compounds may comprise those which react with a colour developer oxidation product with elimination of an inhibitor residue to yield a dye (DIR couplers) or those which release the inhibitor without simultaneously forming a dye. The latter are also strictly speaking known as DIR compounds.
DIR couplers are frequently introduced into photographic layers as emulsions. Emulsions are finely divided dispersions of oil in an aqueous medium, wherein the oil droplets then consist of a solution of DIR couplers in a high-boiling solvent, the “oil former”. Conventional oil formers, such as for example tricresyl phosphate, which is very frequently used, are hydrophobic. EP 536 889 does, however, also disclose the use of DIR couplers together with special protic oil formers in green-sensitive silver halide emulsion layers containing pyrazoloazole magenta couplers. According to said application, the special oil formers make it possible to offset the disadvantages of pyrazoloazole magenta couplers, such as poor processing stability.
DIR couplers give rise to a desired increase in the interimage effect in colour photographic materials. DIR couplers may also improve sharpness and grain. However, as a result of development inhibition, the use of DIR couplers also results in an unwanted reduction in sensitivity.
The object underlying the invention is to provide a colour photographic material which contains at least one DIR coupler together with at least one oil former and in which the interimage effect is increased in comparison with the prior art, but in which the use of the DIR coupler brings about no reduction in sensitivity in comparison with the prior art.
The present invention provides a colour photographic recording material having at least one spectrally sensitised silver halide emulsion layer, characterised in that said silver halide emulsion layer contains an oil former having a pKa value of less than 18 and a DIR coupler and the material contains at least one colour coupler which complies with the formulae
in which
R
1
, R
6
, R
9
mean alkyl aryl;
R
2
means chlorine, alkoxy;
R
3
means acyl, acylamino;
R
4
, R
5
, R
8
mean alkyl;
R
7
means aryl;
L
1
means a single bond, —CO—;
Y
1
, means hydrogen, carbamoyloxy;
X
1
means hydrogen, chlorine;
Z
1
means a heterocyclic, nitrogenous, N-linked 5-membered ring;
Z
2
means hydrogen, alkylsulfido, arylsulfido or a heteroaromatic, nitrogenous, N-linked, 5-membered ring;
Z
3
means hydrogen, chlorine, alkoxy, aryloxy, alkylsulfido and
p means 1 or 2,
and wherein R
4
and R
5
may form a 5- or 6-membered ring.
The pK
3
values of the oil formers are determined by titration with tetrabutyl-ammonium hydroxide (TBAH) in dimethyl sulfoxide/water (100:0.25), as described in “Acid Base Titrations in Nonaqueous Solvents”, Allyn and Bacon Inc., Boston 1973 and in W. Huber “Titration in nichtwässrigen Lösungsmitteln”, Akademische Verlagsgesellschaft, Frankfurt am Main 1964.
It has surprisingly been found that an increased interimage effect is achieved with the embodiment of the photographic material according to the invention, without any reduction in sensitivity.
Compounds (K-1) to (K-20) are examples of suitable couplers of the formulae (K-I), (K-II), (K-III), (K-IV) and (K-V).
Particularly preferred colour couplers are of the formula (K-III).
Suitable DIR couplers for the purposes of the present invention may be found in Research Disclosure 37254, part 5 (1995), page 290, in Research Disclosure 37038, part XIV (1995), page 86 and in Research Disclosure 38957, part X c (1996), page 618.
In a preferred embodiment, the DIR coupler complies with the formula (D-I),
wherein
Q
1
means the remaining members to complete a fused and optionally substituted benzene or heteroaromatic ring;
X
1
means O or NR
2
;
R
1
means alkyl, aryl, hetaryl or alkenyl;
R
2
means H or R
1
;
INH means
Time means a linking member which, on reaction of the coupler with the oxidation product of a silver halide developer, is released together with the residue INH attached thereto and in turn releases the residue INH with a delay under development conditions;
R
11
, R
12
mean H, alkyl, aryl, alkaryl, —S—R
13
, —COO—R
13
, —CON(R
13
)R
14
, —N(R
15
)R
16
, —OR
13
, or a heterocyclic group;
R
13
, R
14
mean alkyl, aryl, alkenyl or alkynyl;
R
15
means H or R
13
;
R
16
means acyl or R
13
;
R
17
means H, alkyl, aryl or a heterocyclic group and
n means
0
or 1,
wherein at least one of the residues R
11
or R
12
is not H and R
11
and R
12
, R
13
and R
14
or R
15
and R
16
may form a five- to seven-membered ring.
Particularly preferred compounds (D-I) are those in which INH denotes
The present invention also provides a colour photographic recording material having at least one spectrally sensitised silver halide emulsion layer, characterised in that said silver halide emulsion layer contains an oil former having a pKa value of less than 18 and a DIR coupler which is of the formula
A
1
&Parenopenst;Time&Parenclosest;
n
INH (D-II)
wherein
A
1
is of the formula
or corresponds to the residue of a malonic acid diester, malonic acid diamide or malonic ester amide yellow coupler, of an acylacetamide or -anilide yellow coupler, of an anilino- and acylaminopyrazolone magenta coupler, of a pyrrolotriazole or pyrrolobenzimidazole magenta coupler, of a 2-acylamino-, 2,5-diacylamino- or 2-ureido-5-acylaminophenol cyano coupler or of a 2-acyl- or
2-acyl-5-acylaminonaphthol cyan coupler, which couples with the oxidation product of a silver halide developer under the conditions of photographic development and so releases the residue of the formula
&Parenopenst;Time&Parenclosest;
n
INH;
INH means
Time means a linking member which, on reaction of the coupler with the oxidation product of a silver halide developer, is released together with the residue INH attached thereto and in turn releases the residue INH with a delay under development conditions;
R
11
, R
12
mean H, alkyl, aryl, alkaryl, —S—R
13
, —COO—R
13
, —CON(R
13
)R
14
, —N(R
15
)R
16
, —OR
13
, or a heterocyclic group;
R
13
, R
14
mean alkyl, aryl, alkenyl or alkynyl;
R
15
means H or R
13
;
R
16
means acyl or R
13
;
R
17
means H, alkyl, aryl or a heterocyclic group;
n means 0 or 1;
Q
31
means the remaining members to complete a fused and optionally substituted benzene or heteroaromatic ring;
X
31
means O or NR
32
;
R
31
means alkyl, aryl, hetaryl or alkenyl and
R
32
means H or R
31
, and
wherein at least one of the residues R
11
or R
12
is not H and R
11
and R
12
, R
13
and R
14
or R
15
and R
16
may form a five- to seven-membered ring.
In a preferred embodiment, the compounds are of the formula (D-II), in which
R
11
and R
12
denote H, alkyl, aryl, —SR
13
, —COO—R
13
, —COON(R
13
)R
14
or —O—R
13
and
R
13
, R
14
denote alkyl, aryl or alkynyl.
Particularly preferably, the compounds are of the formula (D-II), in which INH denotes
In another preferred embodiment, the coupler residue A
1
denotes a residue of the formula (D-III) or the residue of a benzoylacetanilide yellow coupler, of an anilino- or acylaminopyrazolone magenta coupler, of a pyrrolotriazole or pyrrolobenzimidazole magenta coupler, of a 2-acylamino-, 2,5-diacylamino- or 2-ureido-5-acylaminophenol cyan coupler, or of a 2-acyl-5-acylaminonaphthol cyan coupler.
It has surprisingly been found that an increased interimage effect is also achieved with this embodiment of
Büscher Ralf
Hagemann Jörg
Helling Günter
Wiesen Heinz
Wirowski Ralf
Agfa-Gevaert
Connoly Bove Lodge & Hutz LLP
Letscher Geraldine
LandOfFree
Color photographic silver halide 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 silver halide material, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Color photographic silver halide material will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2828833