Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
2001-07-27
2002-09-17
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S607000, C430S613000, C430S599000, C430S600000, C430S555000
Reexamination Certificate
active
06451520
ABSTRACT:
This invention relates to a colour photographic silver halide material which exhibits improved granularity.
Colour photographic materials, particularly colour films, should have a granularity which is as fine as possible. However, since they should also have a high sensitivity to light, and increasing their sensitivity to light usually results in the enlargement of the silver halide grains which in turn has an adverse effect on granularity, it is often impossible to produce fine-grained colour photographic materials of high sensitivity.
Attempts have been made to overcome this disadvantage by employing certain benz-imidazoles (DE 195 07 913); however, this has resulted in an increase in fogging. 1-dodecyl-2-methylimidazole (U.S. Pat. No. 4,585,728, compound No. 18) exhibits what are merely unsatisfactory values of granularity and sensitivity.
The object of the present invention was to improve granularity without loss of sensitivity and without an increase in fogging.
It has now surprisingly been found that this object can be achieved by the addition of certain imidazoles.
The present invention therefore relates to a colour photographic silver halide material comprising a support and at least one silver halide emulsion layer which is deposited thereon and which contains at least one colour coupler, characterised in that said layer also contains a compound of formula (I)
wherein
R
1
denotes alkyl, aryl, aralkyl or hetaryl,
R
2
denotes H or R
1
, or
R
1
and R
2
together denote the remaining members of a heterocyclic ring,
R
3
, R
4
, independently of each other, denote aryl or hetaryl or together denote the remaining members of a phenanthrene ring which is condensed-on in the 9,10-position,
wherein R
1
can also be H if R
3
and R
4
together form a phenanthrene ring.
The aforementioned substituents can be substituted by halogen, hydroxy, alkoxy, amino, acylamino, alkoxycarbonyl and aininosulphonyl; aryl can be substituted by aralkyl in the aryl part, and hetaryl can also be substituted by alkyl.
In particular, the compound of formula (I) is used in the respective layer in an amount ranging from 0.1 to 3.0 mol, preferably 0.5 to 1.2 mol/mol coupler.
The compound of formula (I) is preferably dissolved or dispersed, together with the colour coupler, in a high-boiling organic solvent; the solution or dispersion is then emulsified in an aqueous solution of a binder, usually in an aqueous solution of gelatine.
The compound of formula (I) is preferably used together with a 2-equivalent magenta coupler of the pyrazolone series, which has a molecular weight between 500 and 1500 and is used in an amount of 0.3 to 1.5 g/m
2
.
Preferred pyrazolone couplers correspond to formula (II)
wherein
R
5
denotes a substituent from the series comprising aryl, alkylsulphoxyl, aryl-sulphoxyl, acyl, halogen, acylamino, aminosulphonyl, alkylsulphonyl, aryl-sulphonyl, sulphonamido, imido, carbamato, heteroacylyl, alkylthio, carboxyl or hydroxyl,
R
6
denotes a substituent from the group comprising halogen, CN, allylsulphonyl, arylsulphonyl, sulphamoyl, sulphamido, carbamoyl, carbonamido, alkoxy, acyl-oxyl, aryloxy, alkoxycarbonyl, ureido, nitro, alkyl, perchloryl and trifluoro-methyl,
X denotes a cleavage group,
Y denotes a direct bond or CO, and
o and p denote 0 or a number from 1 to 5,
wherein if o and/or p>1, the substituents R
5
and R
6
can be identical or different.
The preferred cleavage groups are halogen, alkoxy, aryloxy, alkylthio, arylthio, acyloxy, sulphonarnido, sulphonyloxy, carbonamido, arylazo, imido, heterocyclene radicals which contain nitrogen, and hetarylthio radicals.
Particularly preferred magenta couplers correspond to formula (III)
wherein
R
5
and R
6
have the meanings given above,
R
7
denotes hydrogen or an organic radical,
R
8
denotes acylamino or sulphonylamino,
R
9
denotes chlorine or a C
1
-C
4
alkoxy group, and
r and q, independently of each other, denote 0, 1 or 2.
Suitable couplers of formulae (II) and (III) include:
The compounds of formula I according to the invention can also be used in combination with yellow or cyan couplers and improve the sensitivity/granularity ratio there also.
The preferred compounds of formula (I) correspond to formulae (Ia) and (Ib) given below, wherein R
1
and R
2
have the meanings given above.
Suitable compounds of formula (Ia):
No.
R
1
R
2
1
n-C
6
H
13
H
2
n-C
12
H
25
H
3
n-C
16
H
33
H
4
n-C
12
H
25
5
—(CH
2
)
11
—
6
—(CH
2
)
3
—O—CH
2
CH(C
2
H
5
)C
4
H
9
H
7
—CH
3
—S—C
12
H
25
8
—C
16
H
33
9
n-C
12
H
25
10
11
-isoC
13
H
27
H
12
H
13
—CH
2
CH
2
CN
14
H
15
16
-nC
6
H
13
H
17
-nC
12
H
25
18
—C
2
H
5
19
Suitable compounds of formula (Ib):
No.
R
1
R
2
20
H
21
H
22
H
23
H
24
H
-nC
10
H
23
25
n-C
6
H
13
H
The compounds according to the invention can be prepared by methods which are generally known. For example, they can be prepared as shown in Scheme 1 by the alkylation of a protic imidazole, or can be prepared in a particularly simple manner as shown in Scheme 2 by a multi-component reaction in which unsubstituted to tetra substituted imidazoles are obtained directly.
Synthesis of Compound 3
A mixture of 212 g benzil, 268 g hexadecylamine, 25 g hexamethylenetetramine and 155 g ammonium acetate was stirred at 80° C. for 4 hours in 500 ml glacial acetic acid. After cooling to room temperature, 1000 ml water and 1000 ml methanol were added and the batch was stirred for 2 hours.
The precipitate was filtered off and was washed successively with 2000 ml of a mixture of methanol/water (1:1), and then with 1500 ml methanol. Thereafter, the precipitate was stirred with 3000 ml methanol, filtered off and washed with 1500 ml methanol.
After drying, 309 g (69.5% theoretical) of compound 3 were obtained.
Examples of colour photographic materials include colour negative films, colour reversal films, colour positive films, colour photographic paper, colour reversal photographic paper, and colour-sensitive materials for the colour diffusion transfer process or the silver halide bleaching process.
Photographic materials consist of a support on which at least one light-sensitive silver halide emulsion layer is deposited. Thin films and foils are particularly suitable as supports. A review of support materials and of the auxiliary layers which are deposited on the front and back thereof is given in Research Disclosure 37254, Part 1 (1995), page 285 and in Research Disclosure 38957, Part XV (1996), page 627.
Colour photographic materials usually contain at least one red-sensitive, at least one green-sensitive and at least one blue-sensitive silver halide emulsion layer, and optionally contain intermediate layers and protective layers also.
Depending on the type of photographic material, these layers may be arranged differently. This will be illustrated for the most important products:
Colour photographic films such as colour negative films and colour reversal films comprise, in the following sequence on their support: 2 or 3 red-sensitive, cyan-coupling silver halide emulsion layers, 2 or 3 green-sensitive, magenta coupling silver halide emulsion layers, and 2 or 3 blue-sensitive, yellow-coupling silver halide emulsion layers. The layers of identical spectral sensitivity differ as regards their photographic speed, wherein the less sensitive partial layers are generally disposed nearer the support than are the more highly sensitive partial layers.
A yellow filter layer is usually provided between the green-sensitive and blue-sensitive layers, to prevent blue light from reaching the layers underneath.
The options for different layer arrangements and their effects on photographic properties are described in J. Inf. Rec. Mats., 1994, Vol. 22, pages 183-193, and in Research Disclosure 38957, Part M (1996), page 624.
Colour photographic paper, which as a rule is less sensitive to light than is colour photographic film, usually comprises the following layers on the support, in the following sequence: a blue-sensitive, yellow-coupling silver halide emulsion layer, a green-sensitive, magenta coupling silver halide emulsio
Dahlhaus Uwe
Langen Hans
Odenwälder Heinrich
Agfa-Gevaert
Connolly Bove & Lodge & Hutz LLP
Letscher Geraldine
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