Colour photographic silver halide material

Details Colour photographic silver halide material Colour photographic silver halide material

2003-07-02

2004-08-31

Letscher, Geraldine (Department: 1752)

Radiation imagery chemistry: process, composition, or product th

Radiation sensitive product

Identified radiation sensitive composition with color...

C430S552000, C430S384000, C430S385000

Reexamination Certificate

active

06783924

ABSTRACT:

The invention relates to a colour photographic silver halide material comprising a novel cyan coupler and a chloride-rich silver halide emulsion which is particularly suitable as copying material.
Colour photographic copying materials are, in particular, materials for images to be viewed by reflection or displays which generally have a positive image. They are therefore not recording materials such as colour photographic films.
Colour photographic copying materials conventionally contain 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.
Photographic copying material, such as colour photographic paper, is produced in a few production sites from where it is sent all over the world and is finally processed by exposure and processing into colour photographic prints. Between production and processing the material is stored for different lengths of time and under a wide variety of conditions. Cold storage and cold transportation prescribed by the producer not only result in high costs but are also frequently not adhered to, This is detrimental to the quality of the colour prints and leads to complaints.
There is therefore a need to produce colour photographic materials, in particular colour photographic paper, which does not require cold storage and also does not exhibit sensitometric changes, in particular in the red-sensitive layers, over a prolonged period of storage at 20 to 50° C.
It is known from DE 19 634 385 that, by combining a certain pentamethine cyanin red sensitiser with at least two specific stabilisers, the stability in storage, in particular the gradation stability, of unprocessed colour copying material, may be improved. However, this measure leads to unsatisfactory latent image stability.
However, in copying material according to the prior art, the latent image stability is still unsatisfactory.
The object of the invention was to overcome the disadvantage described above and to thus obtain materials which have very good latent image stability as well as very good stability in storage. Surprisingly, this has been achieved with the cyan coupler defined hereinafter, chloride-rich silver halide emulsions and certain stabilisers.
The invention therefore relates to a colour photographic silver halide material comprising a substrate, 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, characterised in that the silver halide crystals of the red-sensitive layer have a chloride content of at least 95 mol %, the cyan coupler corresponding to the formula
wherein
R
1
represents a hydrogen atom or an alkyl group,
R
2
represents an alkyl, aryl or hetaryl group
R
3
represents an alkyl or aryl group,
R
4
represents an alkyl, alkenyl, alkoxy, aryloxy, acyloxy, acylamino, sulphonyloxy, sulphamoylamino, sulphonamido, ureido, hydroxycarbonyl, hydroxycarbonylamino, carbamoyl, alkylthio, arylthio, alkylamino or arylamino group or a hydrogen atom and
Z represents a hydrogen atom or a group which may be split off under the conditions of chromogenic development and
the red-sensitive layer contains at least one compound of formula
wherein
R
5
represents H, CH
3
or OCH
3
,
R
6
represents H, OH, CH
3
, OCH
3
, NHCO—R
7
, COOR
7
, SO
2
NH
2
, NHCONH2 or NHCONH—CH
3
and
R
7
represents C
1
to C
4
alkyl
The compound (II) is preferably added in an amount of 50 to 5,000 mg per kg Ag and particularly preferably in an amount of 200 to 2,000 mg per kg Ag of the red-sensitive layer.
The cyan coupler particularly preferably corresponds to the formula
wherein
R
8
represents a hydrogen atom or an alkyl group
R
9
represents OR
10
or NR
11
R
12
,
R
10
represents an unsubstituted or substituted alkyl group with 1 to 6 carbon atoms,
R
11
represents an unsubstituted or substituted alkyl group with 1 to 6 carbon atoms,
R
12
represents a hydrogen atom or an unsubstituted or substituted alkyl group with 1 to 6 carbon atoms,
R
13
represents an unsubstituted or substituted alkyl group and
Z represents a hydrogen atom or a group which may be split off under the conditions of chromogenic development,
wherein the total number of carbon atoms of the alkyl groups R
10
to R
13
in a coupler molecule is 8 to 18.
The alkyl groups can be straight chain, branched or cyclic and the alkyl, aryl and hetaryl groups can be substituted, for example, by alkyl, alkenyl, alkyne, alkylene, aryl, heterocyclyl, hydroxy, carboxy, halogen, alkoxy, aryloxy, heterocyclyloxy, alkylthio, arylthio, heterocyclylthio, alkylseleno, arylseleno, heterocyclylseleno, acyl, acyloxy, acylamino, cyano, nitro, amino, thio or mercapto groups,
wherein a heterocyclyl represents a saturated, unsaturated or aromatic heterocyclic radical and an acyl represents the radical of an aliphatic, olefinic or aromatic carboxylic, carbamic, carbonic, sulphonic, amidosulphonic, phosphoric, phosphonic, phosphorous, phosphinic or sulphinic acid.
Preferably the alkyl groups can be substituted, for example, by alkyl, alkylene, hydroxy, alkoxy or acyloxy groups and most preferably by hydroxy or alkoxy groups. Preferred substituents for aryl and hetarylgroups are halogen, in particular Cl and F, alkyl, fluorinated alkyl, cyano, acyl, acylamino or carboxy groups.
Suitable cyan couplers are:
I-1

I-2

I-3

I-4

I-5

I-6

I-7

I-8

I-9

I-10

I-11

I-12

I-13

I-14

I-15

I-16

I-17

I-18

I-19

I-20

I-21

I-22

I-23

I-24

I-25

I-26

I-27

I-28

I-29

I-30

I-31

I-32

I-33

I-34

I-35

I-36

I-37

I-38

I-39

I-40
Synthesis of Couplers I-10
Synthesis of the Phenolic Coupler Intermediate Stage
A solution of 185 g (0.87 mol) 3,4-dichlorobenzoylchloride 2 in 50 ml N-methylpyrrolidone was added dropwise while stirring to 165 g (0.87 mol) 2-amino-4-chloro-5-nitrophenol 1 in 500 ml N-methylpyrrolidone. The mixture was subsequently stirred for 1 hour at ambient temperature and then for 2 hours at 60 to 65° C. After cooling 500 ml water were slowly added and suction filtered. The mixture was then stirred twice with water, then twice with methanol and suction filtered.
Yield 310 g (98%) 3.
A mixture of 310 g (0.86 mol) 3, 171 g iron powder, 2.2 l ethanol and 700 ml N-methylpyrrolidone were heated to 65° C. while stirring. The heating bath was removed and 750 ml concentrated hydrochloric acid were added dropwise within 2 hours. The mixture was then refluxed for 1 hour. After cooling, 1 l water was added and suction filtered, the mixture washed with 2 N hydrochloric acid then with water until the discharge water was colourless. The residue was stirred with 1:5 l water, neutralised by the addition of sodium acetate and suction filtered. The mixture was stirred again twice with 1.5 l methanol and suction filtered.
Yield 270 g (95%) 4.
Synthesis of the Ballast Residue
320 g (3.6 mol) 45% sodium hydroxide solution were added dropwise while stirring within 1 hour to a mixture of 520 g (3.6 mol) 4-chlorothiophenol 5 and 652 g (3.6 mol) 2-bromoethylbutyrate 6 in 1 l ethanol. The reaction was strongly exothermic, the temperature was kept at 75 to 80° C. by cooling, and the mixture was then refluxed for 1 hour. A further 400 g (4.5 mol) sodium hydroxide solution were slowly added (weakly exothermic). After a further 2 hours of refluxing the mixture was cooled and 1 l water was added to it. The mixture was then extracted twice with 250 ml toluene, and the purified organic phases were dried and evaporated on the rotary evaporator. The viscous oil 7 (830 g, still containing toluene) was further reacted without purification.
760 ml hydrogen peroxide (35%) were added dropwise to a solution of 830 g (3.6 mol) of compound 7 and 10 ml sodium tungstate solution (20%)

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