DE1772137A1 - Production of color photographic images - Google Patents

Description

PATENT DEPARTMENT LEVERKUSEN

Za / ax 11.11.1969

Rewriting

Production of color photographic images

The invention relates to a photographic material and a Process for the production of color photographic images by the silver dye bleaching process.

It is known to produce color photographic images by the silver dye bleaching process. In this case, the dye (or the dyes of a multilayer material), usually an azo dye, is bleached image-wise in a strongly acidic bath in a homogeneously colored colloid layer at the points where an over image was previously produced.

Both negatives and reversal images can be produced using this process getting produced. If you get positive paper images or duplicate positives from slides, you work with them a simple black-and-white expansion to generate the! Jllber-

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image, which then represents a negative of the master copy. There the one in the layer (or the three 3-layers of a multicolor material) homogeneously distributed image dye is destroyed in accordance with the silver image, the desired result is ultimately obtained positive paraffin image as a template (reverse image). If a silver image is generated that is positive for the template (oil reversal image) z. B. by a black-and-white reversal development or by means of the bromine ion diffusion process, so arises after the pale bleaching a pigment image that is opposite in gradation to the original, d. H. a positive color image if the original is a parbo negative.

It is very difficult to use the silver color bleaching process to produce color images with sufficiently fine parquet grain and sufficiently flat gradation. A further disadvantage of the Zilutr dye bleaching process is that the azo dyes contained in the silver: ialo =; enide emulsion layers absorb in the same wavelength range in which the silver halide is also photosensitive. This greatly reduces the sensitivity of the layers. For this reason, the known materials for the silver dye bleaching process are only suitable as copying materials and even in this use are inferior to the conventional photographic copying materials.

The invention is based on the object, the .Silber color bleaching process by selecting certain silver halide emulsion :!

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and to modify certain process variants so that color images with fine grain and flat gradation are as high as possible Sensitivity of the silver halide emulsion layer can be obtained.

It has now been found that such emulsions are particularly useful for photographic materials for the silver dye bleaching process are suitable in which the ratio of silver (in the form of silver halide) to the bleachable azo dye is at least 12: 1 per ™ Azo bond and the development was carried out with a phenylenediamine series developer at a relatively high sulfite concentration will.

Highly sensitive silver bromide iodide gelatin emulsions are preferably used. The silver dye ratio of 12: 1 according to the invention is far above the amount of silver required for bleaching an azo dye bond according to the equation e

- N = N - + 4 Ag + 4 H ⁺ -4 2 HH ₂ + 4 Ag ⁺

The highly sensitive emulsions contain at least 10 g of silver in the form of silver halide per 1 kg of raw emulsion. Preferably Work is carried out with emulsions, the silver content of which is 20-3Og Ag per 1 kg of crude emulsion, corresponding to a silver dye ratio of approx. 16: 1 to approx. 25: 1 per azo bond, depending on the molecular weight of the azo dyes used.

009885/0902

The development is carried out with a coloring developer of the p-phenylenediamine series, preferably with one of the following: Ν, Ν-diethyl-p-phenylenediamine, compounds of German Patent 965 617, 4- (N, N-diethylanino) -2-methyl- 'aniline or 4- (N-ethyl-N-raethylsulfamido-ethylamino-2-methylar; iline and the like. The concentration is generally between 0.5-25 g / liter of developer solution, preferably between 2 g and 15 g / liter.

The sulfite content of the developer solutions is compared to that with the same substances for the color development of color materials with incorporated color couplers, the usual developer solutions are much higher and are approx. 15 - 60 g instead of 2.5 - 4.0 g Sulphite per 1 liter of solution, preferably 20-30 g. Such amounts of Gulfit are extraordinarily unusual and in processing harmful to conventional color photographic materials. (β. the article by K. Meyer, Bild und Ton (1954) p. 72)

If the described silver color bleach materials are developed after exposure in one of the usual black-and-white developers and then further processed in the same way, the result is unacceptable with the specified halogen silver excess steep gradations and a much coarser color grain. the Appropriate materials are manufactured in the usual way. JtIs underlayment are preferably carriers with the smoothest possible ■ Surface see 3 * pigmented cellulose acetate films suitable.

The silver halide emulsion layers can be used in a known manner Way to be optically and chemically sensitized. SBe can use the known azo dyes, ζ. B. those in the following German patents contain:

(P 14 72 767.4); (P 14 72 781.2);

(P 15 22 354.3); . (A 51 521 IXa / 57b), (P

22 371.9); (P 15 22 375.3); (P 15 22 407.4);

(A 55 771 IXa / 57b); (A 56 095 IXa / 57b);

(A 57 670 IXa / 57b).

The layers can also be stabilized in a known manner. You can use the known plasticizers, wetting agents or Hardeners included.

After development, further processing is carried out in a known manner.

Example 1

A silver dye bleach material according to the invention can be manufactured and processed as follows:

To 1000 parts of a highly sensitive Bromjodsilberemulsion consisting of 8 '/ <> gelatin and thy 2,6' fo silver equivalent of silver halide, of which 6 '/> as silver iodide successively 50 parts of at 4O ⁰ C a 1' ^ aqueous solution of 6 -Methyl-4-oxy-l, 3,3a, 7-tetraazaindene, 30 parts of a 0.1 / Sigen methanolic solution of a hot sensitizer according to German Auslegeschrift 1 213 240, Example 11, 250 parts of a 2 , Oigen

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aqueous solution of the blue-green dye

OH NH - CO _ / "" K

I]

HO ₃ S SO ₃ H

SO ₃ H

50 parts of a 7.5% aqueous solution from Japonic and 10 parts of a 5.5% methanolic solution of H, Ii ¹ , N ¹ '-Trie- (acryloyl) -perhydro-triazine-l, 3.5 stirred in, " The ratio silver: dye = 20: 1 instead of theoretically 4! 1 based on the bleaching reaction of an azo-dye.

The red-sensitive emulsion produced in this way is placed on a base from prepared white pigmented cellulose acetate applied so that the layer obtained after drying 1.0 c silver in the form of silver halide per square meter.

Samples of the material obtained in this way are placed behind a red filter and a 3-step gray wedge with a logarithmic increase in value exposed from 0.10 and processed as follows:

1. Develop: 8 minutes off in a bath

NjN-n-Butyl-n-uj-sulfobutylphenylenediamir. 6 5

Hydroxylamine sulfate 4 /;

liatric sulfite 2'd; -

Potassium bromide 1;

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Sodium carbonate 100 g

dissolved to 1000 ml with water

2. Soak: 5 minutes

3. Hardening: 5 minutes in a bath

Formalin (30 # aqueous solution) 70 ml sodium hydrogen carbonate 5 g

Water to 1000 ml

4. '..': 5 minutes

5. Color bleaching: 15 minutes in a bath off

Quinoline 50 ml Sodium hypophosphite 5 g Potassium iodide 10 g Sulfuric acid icons. 75 ml Water to 1000 ml

6. Soak: 5 minutes

7. Bleach-fix: 15 minutes in a bath off

Sodium carbonate sicc. Sodium thiosulfate sicc.

Tetranatriumäthylendiamintetra aeetat

Iron (IIl) chloride WatriuBSulfit sicc, 'Water on

24 G 125 G 26th G 15th G 13th G IGCO

10 Ki πλΑ, κ'η

BATH

In the sensitometric evaluation of the color wedge obtained, the maximum density of 1.95 resulted in a y- 'ated of 0.9. On subjective observation of the blue-green color wedge, no color graininess whatsoever can be determined. An increase in the time in the dye bleach bath 5. does not change the stated sensitometric values.

If the same material is exposed in the same way, 5, 4, 3 or 1 minute in a common p-methylaminophenol hydroquinone developer the composition

la. p-methylaminophenol 1 g

Hydroquinone 3 g

Sodium carbonate sicc. 26 g

Sodium sulfite 13 g

Potassium bromide 1 g

V / ater to 1000 ml

developed and then analogously, as described above! in the baths' 2 to 8 further processed, oo there are color wedges that are marked with maximum densities of 1.68, 1.77, 1.02, 1.88 and 1.92, - // erte

of 3.5, 3.5, 3.5, 3 »2 and 2.4 and one that is even more noticeable Show color graininess.

If the under la. named developer 1: 1 with distilled Diluted with water (developer Ib.) And this in the same amount

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thinned material developed therein for 4, 3, 2 and 1 minute and then further processed in baths 2 to 8 so maximum color densities result with 5, 4 and 3 minutes of development time of 1.90, 1.90, 1.91 and vM / s of 3.1, 3.1, 2.6; the 2 and 1 minute wedges are due to incomplete bleaching not possible to evaluate. The grain size is again significantly coarser than in the case of the color wedge obtained in developer 1.

After the above-mentioned exposure, samples of the described material are each developed for 10 minutes at 20 ^° C. in developer solutions I - V, which are derived from a basic recipe and contain equimolar amounts of different p-phenylenediamine derivatives, and then 'in the baths 2 to 8 with the same times as stated above, the maximum color densities and jT'-values given in Table 1 result. When viewed subjectively with the naked eye, practically no color graininess can be determined in all cases.

Basic solution: sodium salt of ethylene diamine tetracetate

Sodium sulfite sicc. Trisodium Phosphate Potassium Bromide V / ater

Developer I contains 6g, Ν-n-butyl-n-vo-sulfobutyl-

p-phenylenediamine

5 G 20th G IO G 1 G 1000 ml

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Developer II contains 5.25 g ΙΙ, Ν-diethyl-p-phenylenediamine per 1

sulfate

Developer III contains 5.55 g ϊί-ethyl-N-oxäthyl-p-I'irieriylen- per 1

diamine sulfate

Developer IV contains 8.72 g of 2-anino-5 | ll-ethereal-N- (2 · -

methylsulfonamidoethyl) amino] toluene sesquisulfate

Developer V contains 4.27 g of 2-amino-5-diethylamino per 1

toluene monohydrochloride

Table 1 Max. I. Parb density ^ Value II 1.96 1.0 developer III 1.95 0.8 developer IV 1.97 0.7 developer V 2.02 0.8 developer 1.83 1.3 developer

Example 2

To 1000 parts of a highly sensitive Bromjodsilbereaulsion consisting of 80 g of gelatin and 23 g of silver in the form of .'Jilberhalogenid which 6 Mol τ "contains as silver iodide are stirred at 40 ⁰ C successively. 40 parts of a 1 / ii ^ en aqueous solution of 6-methyl-4-oxy-1,3,3a, 7-tetraazaindene, 40 parts of a 0.1 # strength methanolic solution of the green sensitizer 16 of the

German patent specification (A 53 033 IXa / 57b), 200 dividers

a 2 ', - »i ^ en aqueous solution of the purple dye of the? omf." l:

HO ₃ S

A-CT356

N = IJ - / ~ \ - NH. 2 0-V \ - NH-

0O ₃ Ii

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CO

30 parts of a 7 »5 /» strength aqueous solution of saponin and 10 parts of a 5% methanolic solution of N, N ¹ , Ν "-tris- (acryloyl) perhydro-triazine-1,3.5. The silver: dye ratio is then 29: 1, based on the bleaching reaction of an azo bond.

The green-sensitive emulsion produced in this way is applied to the substrate described in Example 1 in such a way that the after

the layer obtained after drying contains 0.90 g of silver per m.

Samples of the material obtained in this way are exposed behind a green filter μ and a stepped gray wedge with a logarithmic increase in blackening of 0.10 and, as indicated in Example 1, processed in baths 1 to 8 and dried

The sensitometric evaluation of the purple step wedge obtained resulted in a maximum parabola density of an average of 1.3 and a / ^ Y / ert of 0.95. Again, when viewed subjectively With your naked eye, practically no parsing was detected will.

If the same material is exposed in the same way and 5 or 1 ™ Minute in the under la. specified p-methylaminophenol hydroquinone developer developed and then, as indicated in Example 1, further processed, the following values are obtained:

Table 2 max BATH A value Development time 1.15 2.2 5 minutes 1.29 2.2 1 minute . 009885 / 090-2 - 11 - AG 356

Again, a clear graininess of color can be determined here as well.

If samples of the same material are exposed in the same way and Developed for 10 minutes in each case in the developers I - V described in Example 1 and further processed there, so result purple step wedges with the maximum color densities and / "values given in Table 3. All samples obtained in this way show a significantly lower color grain than when using the p-methylaminophenol hydroquinone developer.

Table 3 maximum developer 1.35 I. 1.37 II 1.35 III 1.37 IY 1.28 V Example 3

-f

-Value

0.8

0.7

0.75

0.8

0.85

Containing about 1000 parts of a highly sensitive Bromjodsilberemulsion containing 90 g of gelatin and 24 g of silver in the form of silver halide, of which 4 mol .- # than silver iodide are at 4O ⁰ C were successively added 30 parts of a 1 jtigen aqueous solution of 6-methyl-4 -oxy-l, 3,3a, 7-tetraazaindene, 300 parts of a 2% aqueous solution of the yellow dye of the formula:

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SO _S H

N = N_ / V. NH-

-CO.CH = CH, CO-

OH

25 parts of a 7.5 point aqueous solution of saponin and 10 parts a 5% methanolic solution of N, N *, N "-Tris- (acryloyl) -perhydro-triazine. The silver: dye ratio is then, based on the bleaching reaction of an azo bond, approx. 20: 1.

The emulsion produced in this way, which is sensitive to blue light, is applied to the substrate mentioned in Example 1 in such a way that

that after drying the layer contains 0.80 g of silver per m. Samples of the material so obtained, are exposed to white light through a step wedge, which has a logarithmic Schwärzungsanstieg of 0.10 and processed in accordance with Example 1 in the baths 1 bi3. 8

The sensitometric evaluation showed a maximum color density of 0.98 and a / ^ Vert of 0.5. The received yellow step

ti

wedge is practically grainless, the layer becomes v / ied with the same exposure 5 or 1 minute in said p-methylaminophenol hydroquinone developer developed and then further processed as in Example 1, the maximum color densities of 0.94 or 0.96 and / ^ - fourth of 1.8 or 1.6 with a coarser color grain, j

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Example 4

On a base made of prepared white pigmented cellulose acetate the following layers are applied one after the other:

1. The red-sensitive emulsion layer according to Example 1 (silver application 0.95 g silver per m ² )

2. an intermediate gelatin layer

3.- the green-sensitive layer according to example 2 (silver application 0.88 g silver per m)

4. a thin gelatin interlayer

5. a pilter yellow layer of colloidal silver 6 * a thin gelatin intermediate layer 7 * the blue-sensitive emulsion layer according to Example 3

(Silver application 0.78 g silver per m ² ) 8. a thin protective gelatin layer

The silver / pigment ratio in the individual layers is 20: 1, 29: 1 and 20: 1.

Samples of this material are shown with white light behind you Step gray wedge with a logarithmic increase in density of 0.10 exposed and processed as follows:

a) in pools 1-8 (same times) after 3-game 1

b) 6.5 »4, 3 minutes development in p-liethylaminopheriol-HydFO-quinone developer la. of example 1 and further processed in baths 2-3 analogous to a)

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c) 8-minute development in developers 1-5 of Example 1 and analogously a) and b) in baths 2-8 further processed.

The following results are obtained:

IC OO OO

6 min dev . in Ib PP
yellow gradation maxim. Parb density Graininess a) 5 min dev . in Ib bg
PP
yellow 0.75
0.80
0.90 1.86
2 | l5 very low
It
η b) 4 min dev . in Ib bg
PP
yellow 2.4
2.3
2.5 1.83
1.74
2.07 strong
H
N 3 min dev . in Ib bg
PP
yellow 2.3
2.0
2.4 1.83
1.81
2.15 η
H
η developer I. bg
PP
yellow 2.15
1.90
2.15 1.88
1.76
2.10 η
Il
n developer II bg
PP
yellow 2.0
1.95
2.15 1.92
1.85
2.17 Il
η
M. c) developer III bg
PP
yellow 0.6
0.6
0.7 1.91
1.96
2.17 very low
M.
It developer IV bg
PP
yellow 0.7
0.7
0.85 1.85
1.94
2.13 Il
Il
η developer V bg
PP
yellow 0.5
0.5
0.55 1.94
2.02
2.18 Il
Il
N bg
PP
yellow 0.6
0.6
0.65 1.90
1.91
2.15 η
η
η 1.25
1.25- 1.70
1.80
2.03 η
• ι
H

A-C

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BATH ORIGINAL

Claims (2)

Claims G/ A process for the production of colored photographic images by the silver dye bleaching process by exposure of a photographic material with at least one silver halide emulsion layer which contains an azo dye, development, parbleaching of the bleach-fix, characterized in that a silver halide emulsion is used whose wood ratio is silver to the azo bond of the bleachable azo dye is at least 12: 1 and that a developer of the p-phenylenediamine series is developed with a high sulfite content. 2. The method according to claim 1, characterized in that a Silver halide emulsion is used, the silver content (in the form of silver halide) per kg at least 10 g and their Silver dye oil ratio is 16: 1 to 25: 1 per azo bond. 3 · The method according to claim 1, characterized in that ■ A developer is developed that contains 0.5 - 25 g per liter a developer of the p-phenylenediamine series with a Sulphite content of 15-6Og per liter is developed. AG 350 - 16 - 009885/0902 bathroom original