DE3919550A1 - Processing colour photographic material contg. specified coupler cpds. - using biodegradable bleach bath contg. ferric salt, chloride, per-sulphate etc. - Google Patents

Abstract

Processing colour photographic materials having a reflective base and blue- (BS), green- (GS) and red- (RS) sensitive Ag halide (AgX) emulsion coat(s) with associated yellow, magenta and cyan couplers respectively involves development, opt. washing, bleaching, opt. washing, fixing and washing or stabilising. The novel features are that the following components and bleach bath parameters are used: 1) the AgX of the emulsion coats contains min. 80mole-% AgCl; 2) the yellow coupler is an alpha-substd.-alpha -pivalyl-acetanilidin -pivalyl-acetanilide cpd. (I); 3) the magenta coupler is a 1-phenyl-3-anilino -pyrazol-5-one cpd. (II); 4) the cyan coupler is a 2-hydroxyanilide (III); and 5) the bleach bath contains (a) an Fe (III) salt, (b) a chloride, (c) a persulphate, (d) a nitrate, and (e) a OH and/or an amino cpd. The couplers are of the formulae: (I), (II) and (III). R1 = a gp. released during colour coupling, attached by an O or N atom; R2 = Cl or alkoxy; R3 = -NR4-CO-R5, -NR4-SO2-R5, -CO-R6, -SO2-NR4-R5, or -SO2NR4-COR5; R4 = H or alkyl; R5 = alkyl, aralkyl or aroxyalkyl; R6 = alkoxy or alkylamino; R7 = H, halogen or alkoxy; R8 = H, halogen or R9; R9 = H, acylamino, -COOR10, -CO-NR11R12, cycloimido or succinimido; R10 and R12 = alkyl; R11 = H or R12; R13 and R18 = H or a gp. released during colour coupling; R14-16 = H, halogen, alkyl, alkoxy, COOH, alkoxycarbonyl, NO2, aryloxy, CN or acylamino; R17 = alkyl, aryl, alkoxyalkyl, aroxyalkyl, alkoxy or alkyl-or arylamino; R19 = 1-20C alkyl; R20 = H or halogen. USE/ADVANTAGE - The Ag produced by development is converted to AgX without damaging the iamge dyestuff, the bleach bath is fast, remains active and stable for long periods, without sedimentation, can be regenerated and can be disposed of easily, since the components are readily biodegradable.

Description

The invention relates to a method for processing a particular photographic silver halide recording material through the steps developing, Bleaching, fixing and watering, whereby watering whole or can be partially replaced by stabilizing and a special bleaching bath is used.

Achieving high quality color photographic supervision images is both of the materials used (Color negative film, color negative paper) as well as from the applied processing method. Special Requirements are placed on the bleaching bath, through the silver produced during development again is to be converted into silver halide without the Image dyes are damaged. The bleaching bath should in addition, work fast, with regeneration remain active and stable for a long time, no precipitation cause and be easy to dispose of.  

The latter means that the Blleichbadbestandteile should be readily biodegradable.

On the other hand, the related material has to be built up be that the bleaching bath comes to the optimum effect. In particular, the silver halide emulsions are used and to the color coupler special requirements posed.

It has now been found that the above conditions when bleaching a color photographic Materials are met, if as an essential feature the combination of certain material parameters and certain Bleach parameter is maintained.

The invention therefore relates to a method for Processing of color photographic materials with one reflective backing and applied at least a blue-sensitive silver halide emulsion layer, which is associated with a yellow coupler, at least one green-sensitive silver halide emulsion layer containing a magenta coupler is associated and at least one red-sensitive silver halide emulsion layer containing a cyan coupler is associated with the method steps Develop, if necessary water, bleach, if necessary watering, fixing, watering or stabilizing, Drying, characterized by the combination following measures:

• 1) the silver halides of the silver halide emulsion layers contain at least 80 mol%, preferably at least 95 mol% of silver chloride,
• 2) the yellow coupler corresponds to the general formula wherein
  R₁ is a group which can be split off via an oxygen atom or a nitrogen atom and can be split off in color coupling,
  R₂ is chlorine or alkoxy,
  R₃ is -NR₄-CO-R₅, -NR₄-SO₂-R₅, -CO-R₆, -SO₂-NR₄-R₅ or -SO₂NR₄-COR₅,
  R₄ is H or alkyl,
  R₅ is alkyl, aralkyl or aroxyalkyl and
  R₆ is alkoxy or alkylamino,
• 3) the magenta coupler corresponds to the general formula wherein
  R₇ is H, halogen or alkoxy,
  R₈ is H, halogen or R₉,
  R₉ is H, acylamino, -COOR₁₀, -CO-NR₁₁R₁₂, cycloimido or succinimido,
  R₁₀ alkyl,
  R₁₁ is H or R₁₂,
  R₁₂ alkyl,
  R₁₃ H or a group which can be split off in color coupling,
  R₁₄, R₁₅, R₁₆ H, halogen, alkyl, alkoxy, carboxy, alkoxycarbonyl, nitro, aryloxy, cyano or acylamino,
• 4) the cyan coupler corresponds to the general formula wherein
  R₁₇ alkyl, aryl, alkoxyalkyl, aroxyalkyl, alkoxy or alkyl or arylamino;
  R₁₈ H or a group which can be split off in color coupling,
  R₁₉ alkyl having 1 to 20 carbon atoms, and
  R₂₀ is H or halogen,
• 5) the bleaching bath contains the following compounds: a) an iron (III) salt,
  b) a chloride,
  c) a persulfate,
  d) a nitrate and
  e) a hydroxy and / or an amino compound,

Preferably, the bleach contains per liter
0.005 to 0.2 mol of Fe (III) ions, 0.05 to 1 mol of chloride and 0.01 to 0.5 mol of persulfate, 0.05 to 1.5 mol of nitrate ions and 0.001 to 0.5 mol of hydroxy and / or amino compound. In addition, the bleaching bath may contain a complexing agent, preferably in an amount of up to 0.6 mol / l.

The pH of the bleaching bath is preferably less as 3. The bleaching bath is in particular bromide-free, although low bromide levels (less than 5 mole% of the Amount of chloride) will not hurt. Further, the bleach contains preferably no readily biodegradable complexing agents, although these are generally neither the photographic Properties of the material still the stability of the bleaching bath adversely affect.

As iron (III) salt are particularly suitable iron (III) nitrate, iron (III) chloride and iron (III) - Sulfate, because with these salts anions in the bleach come, which arise anyway (for example, sulfate from the Persulfate) or for other reasons.

For the rest, chloride, nitrate and persulfate are expediently added used as alkali or ammonium compound. The use as free acid (hydrochloric acid, Nitric acid) is conceivable, for example, if the desired pH is not adjusted in any other way becomes.  

The bleaching bath usually becomes at a temperature applied from 20 to 40 ° C.

The remaining silver halide next to silver chloride is usually silver bromide.

The processing method can be under constant Regenerate the individual processing solutions continuously To run.

The by R₁, R₁₃ and R₁₈ shown in color coupling cleavable groups are in particular those which the respective couplers the properties of 2-equivalent couplers to lend. It can be different Molecule residues act, including such residues, the after release from the coupler molecule a photographic Unfold their effect. Examples are aryloxy, Sulfoamido or heterocyclic radicals, for example via a ring nitrogen atom to the coupling site of the coupler are bound. At the remains, after release from the coupler molecule, a photographic For example, it can take effect to act on the residues of development inhibitors that directly or via a timed intermediary to the Coupling point of the coupler are bound. R₁ means preferably a group of the formula

in which
R₂₂ is a radical to complete an optionally substituted imidazole, pyrazole, triazole, oxazole, thiazole or thiadiazole ring.

Moreover, the substituents R₂ to R₂₁ have preferred the following meanings:

R₂ Cl or C₁-C₂₀ alkoxy
R₄ is hydrogen,
R₇ chlorine,
R₈ hydrogen,
R₁₁ is hydrogen,
R₁₄, R₁₅, R₁₆ halogen, isnbesondere in 2-, 4- and 6-position, preferably chlorine,

R₁₈ additionally chlorine,
R₁₉ ethyl, propyl, butyl,
R₂₀ chlorine,
R₂₂ is hydrogen or alkyl and
R₂₃, R₂₄ C₁-C₁₆ alkyl.

Suitable cyan couplers (C), magenta couplers (M) and Yellow couplers (Y) are listed below:

The hydroxy compounds present in the bleaching or amino compounds include the following classes of compounds on:

• 1. Carbohydrates / sugar carboxylic acids / sugar alcohols.
• 2. Aliphatic alcohols / glycols.
• 3. Phenols / naphthols / aromatic polyhydroxy compounds.
• 4. Hydroxycarboxylic acids.
• 5. Aliphatic amines / aliphatic diamines.

Suitable hydroxy and amino compounds are, for. B .:

• I. Carbohydrates / sugar carboxylic acid / sugar alcohols
  Glucose, fructose, sucrose, mannose, gluconic acid, sorbitol, mannitol, ascorbic acid, carboxymethylcellulose, dextrin
• II. Alcohols / Glycols
  Glycerine, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1-phenylethanol, glycol, di-, tri-, tetra-, penta-, hexa-, septa-, octaethylene glycol, polyethylene glycol (MW 1550, MW 4000) , 1,6-hexanediol, 1,2-cyclohexanediol
• III. Phenols / naphthols / aromatic polyhydroxy compounds
  Resorcinol, pyrogallol, 1,3,5-trihydroxybenzene, 1-naphthol-2,4,8-trisulfonic acid, hydroquinone-sulfonic acid potassium salt, 2-hydroxybenzenesulfonic acid
• IV. Hydroxycarboxylic acids
  Tartaric acid, citric acid, salicylic acid, 2-hydroxybenzenesulfonic acid.
• V. Amines
  Monoethanolamine, hydroxylamine, diethylhydroxylamine, ethylenediamine, N, N'-dimethylethylenediamine, hexamethylenediamine, propylenediamine, 1,4-cyclohexanediamine, diethylenetriamine, pentaethylenediamine.

Particularly preferred compounds are, for. B .:

Glycerin, ethylene glycol, diethylene glycol;
Glucose, fructose, sorbitol;
Tartaric acid, citric acid, salicylic acid;
Ethylenediamine, propylenediamine, hexamethylenediamine.

In the complexing agents contained in the bleaching solution according to the invention they are aminopolycarboxylic acids and hydroxycarboxylic acids and polycarboxylic acids.

Suitable complexing agents are aminopolycarboxylic acids with a nitrogen atom, e.g. B. nitrilotriacetic acid and their Derivatives.

Further suitable, although difficult to biodegrade, are ethylenediaminetetraacetic acid and its derivatives, 2-hydroxy-propylenediamine (1,3) -tetraacetic acid, diethylenetriaminepentaacetic acid.  

Well suited are tartaric acid, citric acid and salicylic acid.

The hydroxy function of class (e) and the Complexing function can be combined in one connection his.

example

A color photographic recording material which suitable for the processing method according to the invention is made by placing on a substrate on both sides with polyethylene coated paper the following layers in the order given were. The quantities refer to each on 1 m². For the silver halide order, the corresponding Amounts indicated AgNO₃.

layer structure

• 1st layer (substrate layer): 0.2 g of gelatin
• 2nd layer (blue-sensitive layer):
  blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 microns) from 0.63 g of AgNO₃ with 1.38 g of gelatin
  0.95 g yellow coupler Y 40
  0.29 g tricresyl phosphate (TKP)
• 3rd layer (protective layer) 1.1 g of gelatin
  0.06 g of 2,5-dioctylhydroquinone
  0.06 g dibutyl phthalate (DBP)
• 4th layer (green-sensitive layer)
  green-sensitized silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, mean grain diameter 0.6 μm) from 0.45 g AgNO₃ with 1.08 g gelatin
  0.41 g magenta coupler M 13
  0.08 g of 2,5-dioctylhydroquinone
  0.34 g DBP
  0.04 g TKP
• 5th layer (UV protection layer) 1.15 g gelatin
  0.6 g UV absorber of the formula 0.045 g of 2,5-dioctylhydroquinone
  0.04 g TKP
• 6th layer (red-sensitive layer)
  red sensitized silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, mean grain diameter 0.5 μm) from 0.3 g AgNO₃ with 0.75 g gelatin
  0.36 g cyan coupler C 8
  0.36 g TKP
• 7th layer (UV protection layer) 0.35 g of gelatin
  0.15 g of UV absorber according to the 5th layer
  0.2 g TKP
• 8th layer (protective layer) 0.9 g of gelatin
  0.3 g of hardener H of the following formula

Example 1 (Comparative)

A step wedge is applied to the photographic one described above Recording material exposed and how follows processed:

The individual processing baths had the following Composition:

developer Water | 900 ml Ethylenediaminetetraacetic acid (EDTA) 2 g Hydroxyethanediphosphonic acid (HEDP) 60% by weight 0.5 ml sodium chloride 2 g N, N-diethylhydroxylamine, 85% by weight 5 ml 4- (N-ethyl-N-2-methanesulfonylaminoethyl) -2-methylphenylenediamine sesquisulfate monohydrate (CD3), 50% by weight 8 ml potassium carbonate 25 g

pH value adjustment to 10 with KOH or H₂SO₄.
Make up to 1 liter with water.

Bleaching bath A Water | 900 ml potassium persulfate 20 g citric acid 20 g sodium chloride 15 g Iron (III) chloride 7 g

Make up to 1 liter with water.
pH value: approx. 1.

fixer Water | 900 ml sodium 10 g ammonium 100 g

pH adjustment to 7 with ammonia water or Acetic acid. Make up to 1 liter with water.

Rest determination of silver

The exposed and then as described above processed step wedge of photographic material was equipped with a PM 8030 infrared silver detector Company Photo-Matic, Denmark on residual silver in the picture black examined.

The sample contained no residual silver.

Detection of bromine or chlorine release

The liberated bromine or chlorine is by a iodide-containing Filter paper passes and oxidizes it Iodide to iodine. The iodine colors the filter paper yellow. The Intensity of staining is determined with a densitometer and is a measure of the resulting bromine or Amount of chlorine.  

execution

Each 25 ml of the test solution to be examined in a Test tube (length 180 mm, outer diameter 20 mm) given (without rim wetting), with a cap made of filter paper (Feltafilter S No. 1406 1/2 medium fast, white) provided and closed with a rubber band.

corrosion test

100 ml of the test solution are added to a 100 ml Beaker is given. In this solution is a degreased and balanced V2A sheet (100 × 20 × 1 mm) placed in it, that about 3/4 of the sheet is wetted. After 6 days, the sheet is removed from the solution, cleaned and weighed back. The weight loss is through Corrosion arose. For heavily corroded sheets is additionally to detect pitting (samples A and C).

The results regarding chlorine or bromine development and Corrosion can be found in the following tables. The color image produced was typified.

Example 2 (Comparative)

Exposure and processing were as in Example 1 described. The developer and fixer had the same composition as in Example 1.

Bleaching bath B Water | 900 ml potassium persulfate 20 g sodium chloride 20 g Iron (III) nitrate · 9 H₂O 16 g sodium nitrate 20 g

Make up to 1 liter with water.
pH value: approx. 1.

The sample contained no residual silver.

Example 3 (Invention)

Exposure and processing were as in Example 1 described. The developer and fixer had the same composition as in Example 1.

Bleaching bath C Water | 900 ml potassium persulfate 20 g citric acid 20 g sodium chloride 20 g Iron (III) nitrate · 9 H₂O 16 g sodium nitrate 20 g

Make up to 1 liter with water.
pH value: approx. 1.

The sample contained no residual silver.  

Table 1

Densitometer values of yellow density (determination of iodine)

Table 2

Weight loss of V2A sheets

The sheet of Experiment A also showed pitting.

Claims (2)

Claims 1. A method of processing color photographic materials having a reflective support coated thereon with at least one blue-sensitive silver halide emulsion layer associated with a yellow coupler, at least one green-sensitive silver halide emulsion layer having a magenta coupler and at least one red-sensitive silver halide emulsion layer having a cyan coupler attached thereto Developing, optionally watering, bleaching, optionally watering, fixing, watering or stabilizing, drying, characterized by the combination of the following measures:

• 1) the silver halides of the silver halide emulsion layers contain at least 80 mol%, silver chloride,
• 2) the yellow coupler corresponds to the general formula wherein
  R₁ is a group which can be split off via an oxygen atom or a nitrogen atom and can be split off in color coupling,
  R₂ is chlorine or alkoxy,
  R₃ is -NR₄-CO-R₅, -NR₄-SO₂-R₅, -CO-R₆, -SO₂-NR₄-R₅ or -SO₂NR₄-COR₅,
  R₄ is H or alkyl,
  R₅ is alkyl, aralkyl or aroxyalkyl and
  R₆ is alkoxy or alkylamino,
• 3) the magenta coupler corresponds to the general formula wherein
  R₇ is H, halogen or alkoxy,
  R₈ is H, halogen or R₉,
  R₉ is H, acylamino, -COOR₁₀, -CO-NR₁₁R₁₂, cycloimido or succinimido,
  R₁₀ alkyl,
  R₁₁ is H or R₁₂,
  R₁₂ alkyl,
  R₁₃ H or a group which can be split off in color coupling,
  R₁₄, R₁₅, R₁₆ H, halogen, alkyl, alkoxy, carboxy, alkoxycarbonyl, nitro, aryloxy, cyano or acylamino,
• 4) the cyan coupler corresponds to the general formula wherein
  R₁₇ alkyl, aryl, alkoxyalkyl, aroxyalkyl, alkoxy or alkyl or arylamino;
  R₁₈ H or a group which can be split off in color coupling,
  R₁₉ alkyl having 1 to 20 carbon atoms, and
  R₂₀ is H or halogen,
• 5) the bleaching bath contains the following compounds: a) an iron (III) salt,
  b) a chloride,
  c) a persulfate,
  d) a nitrate and
  e) a hydroxy and / or an amino compound.

2. The method according to claim 1, characterized in that the bleaching bath per liter contains: 0.005 to 0.2 mol Fe (III) ions,
From 0.05 to 1 mole of chloride,
0.01 to 0.5 moles of persulfate,
0.05 to 1.5 moles of nitrate ions,
0.001 to 0.5 mole of hydroxy and / or amino compound and
up to 0.6 mol complexing agent.