Production of a color photographic image

This invention relates to the production of a colour photographic image in a continuous process comprising at least the stages a) treatment with a bath containing H.sub.2 O.sub.2 or a bath containing a compound which liberates H.sub.2 O.sub.2 and b) fixing, wherein stage b) immediately follows stage a).
When a process in which a conventional fixing bath immediately follows an intensifying bath or bleaching bath containing H.sub.2 O.sub.2 is performed continuously, silver oxide and silver precipitation occurs after a short time, which is deposited on the transport rollers and then soils the photographic material.
The object of the invention is to avoid this disadvantage.
It has now been found that this disadvantage may be avoided if, during the continuous process, a molar ratio of anti-oxidant to fixing agent of >0.2 is maintained and the fixing bath contains a buffer substance in a quantity of >0.4 mol/l.
Preferred embodiments of the invention are when the molar ratio of antioxidant to fixing agent is >0.25 and the buffer substance is present in a quantity of >0.6 mol/l.
Suitable anti-oxidants are sulphites and sulphinates.
Suitable fixing agents are thiosulphates, halides and thiocyanates, with alkali metal and ammonium thiosulphates being preferred.
The buffer substances should in particular buffer a pH value range from 5 to 9.
Preferred buffer substances are mono- and polycarboxylic acids, carbonates, phosphonates and phosphates.
The process according to the invention is suitable for all conventional colour photographic materials, but may be used particularly advantageously with low-silver materials having a silver halide application rate of .gtoreq.0.50 g/m.sup.2 (as Ag) and an AgCl content of the emulsion of greater than 95 mol. %.
Examples of colour photographic materials are colour negative films, colour reversal films, colour positive films, colour photographic paper, colour reversal photographic paper, colour-sensitive materials for the dye diffusion transfer process or the silver dye bleaching process.
The photographic 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 thereof is given in Research Disclosure 37254, part 1 (1995), page 285.
The colour photographic 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 material, these layers may be differently arranged. This is demonstrated for the most important products:
Colour photographic films such as colour negative films and colour reversal films have on the support, in the stated sequence, 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 with regard to their photographic sensitivity, wherein the less sensitive partial layers are generally arranged closer to the support than the more highly sensitive partial layers.
A yellow filter layer is conventionally arranged between the green-sensitive and blue-sensitive layers to prevent blue light from reaching the underlying layers.
Possible options for different layer arrangements and the effects thereof on photographic properties are described in J. Inf. Rec. Mats., 1994, volume 22, pages 183-193.
Colour photographic paper, which is usually substantially less photosensitive than a colour photographic film, conventionally has on the support, in the sequence stated below, 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; the yellow filter layer may be omitted.
The number and arrangement of the photosensitive layers may be varied in order to achieve specific results. For example, all high sensitivity layers may be grouped together in one package of layers and all low sensitivity layers may be grouped together another package of layers in order to increase sensitivity (DE 25 30 645).
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 286.
Details of suitable silver halide emulsions, the production, ripening, stabilisation and spectral sensitisation thereof, including suitable spectral sensitisers, may be found in Research Disclosure 37254, part 3 (1995), page 286 and in Research Disclosure 37038, part XV (1995), page 89.
Photographic materials with camera sensitivity conventionally contain silver bromide-iodide emulsions, which may optionally also contain small proportions of silver chloride. Photographic print materials contain either silver chloride-bromide emulsions with up to 80 wt. % of AgBr or silver chloride-bromide emulsions with above 95 mol. % of AgCl.
Details relating to colour couplers may be found in Research Disclosure 37254, part 4 (1995), page 288 and in Research Disclosure 37038, part II (1995), page 80. The maximum absorption of the dyes formed from the couplers and the developer oxidation product is preferably within the following ranges: yellow coupler 430 to 460 nm, magenta coupler 540 to 560 nm, cyan coupler 630 to 700 nm.
In order to improve sensitivity, grain, sharpness and colour separation in colour photographic films, compounds are frequently used which, on reaction with the developer oxidation product, release photographically active compounds, for example DIR couplers which eliminate a development inhibitor.
Details relating to such compounds, in particular couplers, may be found in Research Disclosure 37254, part 5 (1995), page 290 and in Research Disclosure 37038, part XIV (1995), page 86.
Colour couplers, which are usually hydrophobic, as well as other hydrophobic constituents of the layers, are conventionally dissolved or dispersed in high-boiling organic solvents. These solutions or dispersions are then emulsified into an aqueous binder solution (conventionally a gelatine solution) and, once the layers have dried, are present as fine droplets (0.05 to 0.8 .mu.m in diameter) in the layers.
Suitable high-boiling organic solvents, methods for the introduction thereof into the layers of a photographic material and further methods for introducing chemical compounds into photographic layers may be found in Research Disclosure 37254, part 6 (1995), page 292.
The non-photosensitive interlayers generally located between layers of different spectral sensitivity may contain agents which prevent an undesirable diffusion of developer oxidation products from one photosensitive layer into another photosensitive layer with a different spectral sensitisation.
Suitable compounds (white couplers, scavengers or DOP scavengers) may be found in Research Disclosure 37254, part 7 (1995), page 292 and in Research Disclosure 37038, part III (1995), page 84.
The photographic material may also contain UV light absorbing compounds, optical whiteners, spacers, filter dyes, formalin scavengers, light stabilisers, anti-oxidants, D.sub.min dyes, additives to improve stabilisation of dyes, couplers and whites and to reduce colour fogging, plasticisers (latices), biocides and others.
Suitable compounds may be found in Research Disclosure 37254, part 8 (1995), page 292 and in Research Disclosure 37038, parts IV, V, VI, VII, X, XI and XIII (1995), pages 84 et seq.
The layers of colour photographic materials are conventionally hardened, i.e. the binder used, preferably gelatine, is crosslinked by appropriate chemical methods.
Suitable hardener substances may be found in Research Disclosure 37254, part 9 (1995), page 294 and in Research Disclosure 37038, part XII (1995), page 86.
Once exposed with an image, colour photographic materials are processed using different processes depending upon their nature. Details relating to processing methods and the necessary chemicals are disclosed in Research Disclosure 37254, part 10 (1995), page 294 and in Research Disclosure 37038, parts XVI to XXIII (1995), pages 95 et seq. together with example materials.
According to the invention, however, the material is passed through a fixing bath, which immediately follows a bath which contains H.sub.2 O.sub.2 or an H.sub.2 O.sub.2 -liberating compound.

EXAMPLE 1
A colour photographic recording material, which contained the following layers applied in the stated sequence onto a paper coated on both sides with polyethylene, wherein all quantities are stated per 1 m.sup.2 and the quantities of silver are stated as AgNO.sub.3, was exposed with an image and processed as stated.
1st layer (substrate layer)
0.10 g of gelatine
2nd layer (blue-sensitive layer)
Blue-sensitive silver halide emulsion (99.5 mol. % of chloride and 0.5 mol. % of bromide, average grain diameter 0.9 .mu.m) prepared from
0.50 g of AgNO.sub.3 and
1.25 g of gelatine
0.42 g of yellow coupler Y-1
0.18 g of yellow coupler Y-2
0.50 g of tricresyl phosphate (TCP)
0.10 g of stabiliser ST-1
0.70 mg of blue sensitiser S-1
0.30 mg of stabiliser ST-2
3rd layer (interlayer)
1.10 g of gelatine
0.06 g of oxform scavenger O-1
0.06 g of oxform scavenger O-2
0.12 g of TCP
4th layer (green-sensitive layer)
Green-sensitised silver halide emulsion (99.5 mol. % of chloride, 0.5 mol. % of bromide, average grain diameter 0.47 .mu.m) prepared from
0.40 g of AgNO.sub.3 and
0.77 g of gelatine
0.41 g of magenta coupler M-1
0.06 g of stabiliser ST-3
0.12 g of oxform scavenger O-2
0.34 g of dibutyl phthalate (DBP)
0.70 mg of green sensitiser S-2
0.50 mg of stabiliser ST-4
5th layer (UV protective layer)
1.15 g of gelatine
0.50 g of UV absorber UV-1
0.10 g of UV absorber UV-2
0.03 g of oxform scavenger O-1
0.03 g of oxform scavenger O-2
0.35 g of TCP
6th layer (red-sensitive layer)
Red-sensitised silver halide emulsion (99.5 mol. % of chloride, 0.5 mol. % of bromide, average grain diameter 0.5 .mu.m) prepared from
0.30 g of AgNO.sub.3 and
1.00 g of gelatine
0.46 g of cyan coupler C-1
0.46 g of TCP
0.03 mg of red sensitiser S-3
0.60 mg of stabiliser ST-5
7th layer (UV protective layer)
0.35 g of gelatine
0.15 g of UV absorber UV-1
0.03 g of UV absorber UV-2
0.09 g of TCP
8th layer (protective layer)
0.90 g of gelatine
0.05 g of optical whitener W-1
0.07 g of polyvinylpyrrolidone
1.20 mg of silicone oil
2.50 mg of spacer (polymethyl methacrylate)
0.30 g of hardener H-1 ##STR1##
______________________________________Bath Temperature Time Replenishment rate______________________________________Development 35.degree. C. 45 s 60 ml/m.sup.2Rinsing 35.degree. C. 120 s 200 ml/m.sup.2Bleaching 35.degree. C. 45 s 250 ml/m.sup.2Fixing 35.degree. C. 30 s 60 ml/m.sup.2Stabilisation 35.degree. C. 60 s 120 ml/m.sup.2______________________________________
______________________________________Developer______________________________________Water 800 mlCD-3 4.5 gPotassium carbonate 27.0 gDiethylhydroxylamine (85 wt. %, 4 mlaqueous)Diethylentriamine pentaacetate 7 ml(40 wt. %, aqueous)Hydroxyethanediphosphonic acid 0.2 ml(50 wt. %, aqueous)KCl 3.2 gOptical brightener W-1 0.8 gAdjust pH to 10.5with KOH, make up to 1 l with water.______________________________________
CD-3 is of the formula: ##STR2##
______________________________________Bleaching bathWater 800 mlDiethylenetriamine pentaacetate 2 ml(40 wt. %, aqueous)Hydroxyethanediphosphonic acid 0.05 ml(60 wt. %, aqueous)Sodium dihydrogen phosphate 4.7 gNaCl 1.5 gH.sub.2 O.sub.2 (35 wt. %) 50 mlAdjust pH to 9.2with KOH, make up to 1 l with water.Fixing bathWater 800 mlAmmonium thiosulphate 1.0 molAnti-oxidant c.f. Table 1Buffer substance c.f. Table 1Ethylenediamine tetraacetate 1.5 gAdjust pH to 7.5with KOH, make up to 1 l with water.Stabilising bathWater 800 mlHydroxyethanediphosphonic acid 0.2 ml(60 wt. %, aqueous)Sodium benzoate 0.6 gAcetic acid 15 mlEthylendiamine tetraacetate 1.5 gAdjust pH to 5.0with KOH, make up to 1 l with water.______________________________________
All the fixing baths fix completely and exhibit no influence upon the photographic result.
TABLE 1______________________________________(Resistance of the fixing bath to precipitation)Anti-oxidant Molar ratio of Buffer(substance) fixing agent to (substance)mol/l anti-oxidant mol/l Precipitation Status______________________________________(1) 0.1 10 (3) 0.4 severe Comparison(1) 0.2 5 (3) 0.4 severe Comparison(1) 0.4 2.5 (3) 0.4 none Invention(1) 0.4 2.5 (3) 0.2 moderate Comparison(1) 0.1 10 (4) 0.4 severe Comparison(1) 0.2 5 (4) 0.4 severe Comparison(1) 0.4 2.5 (4) 0.4 none Invention(1) 0.4 2.5 (4) 0.2 moderate Comparison(2) 0.1 10 (3) 0.4 severe Comparison(2) 0.2 5 (3) 0.4 severe Comparison(2) 0.4 2.5 (3) 0.4 none Invention(2) 0.4 2.5 (3) 0.2 moderate Comparison______________________________________ Substance 1 = Natrium sulphite Substance 2 = Methanesulphinic acid Substance 3 = Sodium hydrogen carbonate Substance 4 = Sodium acetate
EXAMPLE 2
A low-silver material was produced which differed from the material according to Example 1 by changed quantities of silver:
2nd layer: 0.25 g of AgNO.sub.3
4th layer: 0.20 g of AgNO.sub.3
6th layer: 0.15 g of AgNO.sub.3
All other layers are identical to Example 1.
______________________________________ ReplenishmentBath Temperature Time rate______________________________________Development 35.degree. C. 45 s 60 ml/m.sup.2Intensification/bleaching 35.degree. C. 45 s 400 ml/m.sup.2Fixing 35.degree. C. 30 s 60 ml/m.sup.2Stabilisation 35.degree. C. 60 s 120 ml/m.sup.2______________________________________
______________________________________Developer______________________________________Water 800 mlCD-3 6.0 gDeveloper E-1 1.0 gPotassium carbonate 22.0 gDiethylhydroxylamine 4 ml(85 wt. %, aqueous)Diethylenetriamine pentaacetate 7 ml(40 wt. %, aqueous)Hydroxyethanediphosphonic acid 0.2 ml(60 wt. %, aqueous)KCl 3.2 gOptical brightener W-1 0.8 gAdjust pH to 10.5with KOH, make up to 1 l with water.______________________________________
Intensification/bleaching bath
Composition as bleaching bath of Example 1.
______________________________________Fixing bath______________________________________Water 800 mlAmmonium thiosulphate 0.4 molAnti-oxidant c.f. Table 2Buffer substance c.f. Table 2Ethylenediamine tetraacetate 1.5 gAdjust pH to 7.5with KOH, make up to 1 l with water.______________________________________
Stabilising bath
Composition as stabilising bath from Example 1.
All fixing baths fix completely and exhibit no influence on the photographic result.
TABLE 2______________________________________(Resistance of the fixing bath to precipitation) Molar ratio of BufferAnti-oxidant fixing agent to (substance)(substance) anti-oxidant mol/l Precipitation Status______________________________________(1) 0.04 10 (3) 0.4 severe Comparison(1) 0.08 5 (3) 0.4 severe Comparison(1) 0.16 2.5 (3) 0.4 none Invention(1) 0.16 2.5 (3) 0.2 moderate Comparison(1) 0.04 10 (4) 0.4 severe Comparison(1) 0.08 5 (4) 0.4 severe Comparison(1) 0.16 2.5 (4) 0.4 none Invention(1) 0.16 2.5 (4) 0.2 moderate Comparison(2) 0.04 10 (3) 0.4 severe Comparison(2) 0.08 5 (3) 0.4 severe Comparison(2) 0.16 2.5 (3) 0.4 none Invention(2) 0.16 2.5 (3) 0.2 moderate Comparison______________________________________
Developer E-1 is of the formula: ##STR3##
EXAMPLE 3
A colour photographic material according to Example 1 is processed as follows:
______________________________________ ReplenishmentBath Temperature Time rate______________________________________Development 35.degree. C. 3 min 15 s 640 ml/m.sup.2Rinsing 35.degree. C. 120 s 1000 ml/m.sup.2Bleaching 35.degree. C. 5 min 400 ml/m.sup.2Fixing 35.degree. C. 90 s 300 ml/m.sup.2Rinsing 35.degree. C. 120 s 2000 ml/m.sup.2______________________________________
______________________________________DeveloperWater 800 mlCD-4 4.2 gPotassium carbonate 21.0 gHydroxylamine 3.6 gDiethylentriamine pentaacetate 8 ml(40 wt. %, aqueous)Hydroxyethanediphosphonic acid 0.2 ml(60 wt. %, aqueous)Sodium sulphite 3.2 gKBr 3.6 gAdjust pH to 10.1with KOH, make up to 1 l with water.Bleaching bathWater 800 mlDiethylentriamine pentaacetate 2 ml(40 wt. %, aqueous)Hydroxyethanediphosphonic acid 0.05 ml(60 wt. %, aqueous)Sodium dihydrogen phosphate 4.7 g (30 mmol)NaCl 1.5 gH.sub.2 O.sub.2 (35 wt. %) 50 mlAdjust pH to 9.2with KOH, make up to 1 l with water.Fixing bathWater 800 mlAmmonium thiosulphate 0.5 molAmmonium thiocyanate 0.5 molAnti-oxidant c.f. Table 3Buffer substance c.f. Table 3Ethylenediamine tetraacetate 1.5 gAdjust pH to 7.5with KOH, make up to 1 l with water.______________________________________
All the fixing baths fix completely and exhibit no influence on the photographic result.
TABLE 3______________________________________(Resistance of the fixing bath to precipitation)Anti-oxidant Molar ratio of Buffer(substance) fixing agent to (substance)mol/l anti-oxidant mol/l Precipitation Status______________________________________(1) 0.1 10 (3) 0.4 severe Comparison(1) 0.2 5 (3) 0.4 severe Comparison(1) 0.4 2.5 (3) 0.4 none Invention(1) 0.4 2.5 (3) 0.2 moderate Comparison(1) 0.1 10 (4) 0.4 severe Comparison(1) 0.2 5 (4) 0.4 severe Comparison(1) 0.4 2.5 (4) 0.4 none Invention(1) 0.4 2.5 (4) 0.2 moderate Comparison(2) 0.1 10 (3) 0.4 severe Comparison(2) 0.2 5 (3) 0.4 severe Comparison(2) 0.4 2.5 (3) 0.4 none Invention(2) 0.4 2.5 (3) 0.2 moderate Comparison______________________________________
EXAMPLE 4
A colour photographic material according to Example 1 is processed as follows:
______________________________________ ReplenishmentBath Temperature Time rate______________________________________Development 35.degree. C. 3 min 15 s 640 ml/m.sup.2Rinsing 35.degree. C. 120 s 1000 ml/m.sup.2Bleaching 35.degree. C. 4 min 20 s 250 ml/m.sup.2Fixing 35.degree. C. 320 s 100 ml/m.sup.2Rinsing 35.degree. C. 320 s 2000 ml/m.sup.2______________________________________
Developer
Composition as developer from Example 3.
______________________________________Bleaching bathWater 800 ml.beta.-alaninediacetic acid 10 gCitric acid 14 gIron nitrate 8.7 gAcetic acid 60 mlNaCl 21 gPotassium peroxydisulphate 30.7 gAdjust pH to 3.8with KOH, make up to 1 l with water.Fixing bathAmmonium thiosulphate 74.1 gAmmonium thiocyanate 37.5 gAnti-oxidant c.f. Table 4Buffer c.f. Table 4Ethylenediamine tetraacetate 1.5 gAdjust pH to 7.5with KOH, make up to 1 l with water.______________________________________
All the fixing baths fix completely and exhibit no influence on the photographic result.
TABLE 4______________________________________(Resistance of the fixing bath to precipitation)Anti-oxidant Molar ratio of Buffer(substance) fixing agent to (substance)mol/l anti-oxidant mol/l Precipitation Status______________________________________(1) 0.1 10 (3) 0.4 severe Comparison(1) 0.2 5 (3) 0.4 severe Comparison(1) 0.4 2.5 (3) 0.4 none Invention(1) 0.4 2.5 (3) 0.2 moderate Comparison(1) 0.1 10 (4) 0.4 severe Comparison(1) 0.2 5 (4) 0.4 severe Comparison(1) 0.4 2.5 (4) 0.4 none Invention(1) 0.4 2.5 (4) 0.2 moderate Comparison(2) 0.1 10 (3) 0.4 severe Comparison(2) 0.2 5 (3) 0.4 severe Comparison(2) 0.4 2.5 (3) 0.4 none Invention(2) 0.4 2.5 (3) 0.2 moderate Comparison______________________________________

Production of a color photographic image

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