SU465804A3 - A method of obtaining a color photographic image by bleaching a dye with silver - Google Patents

Description

A method of obtaining a color photographic image by bleaching silver dye using photographic material containing a substrate and an "I1Mum one halogen-silver emulsion" layer with a non-diffusing azo dye, is proposed. has the same or higher sensitivity as the azo dye layer. The material is exposed, developed and processed in the presence of a bleach catalyst. The equally high sensitivity of the layers can be achieved by dividing the main emulsion into three parts, adding the dye to one part and pouring the three parts on each other. It is also possible to proceed from different emulsions (with different gradations and different sensitivities) to obtain three layers. silver halide is added to non-dye-containing layers in such an amount per unit of surface that it is equal to or makes up only a fraction of the amount of silver halide introduced into the layer containing the dye, for example, 10-100%. But you can enter and more than 100%. The sensitivity of the dye-free emulsion layer is set in such a way that the color gradation curve becomes linear by straightening the shoulder sections and the base, i.e., it is close to the straight line. By remotely bleaching the upper dye-free layer, the sensitivity of the layer containing the dye at the shoulder area is increased. By remotely bleaching the dye-free bottom layer, it is possible to increase the sensitivity of the dye-containing layer at the base portion. The maximum sensitivity increase with a good alignment of the color gradation curve is achieved when the upper dye-free layer has such high sensitivity that this layer, if it plays the role of a separate additional layer, requires bleaching of the dye with a violation of the linearity of the gradient color curve above the plot caiMbiM, leads to separations, and the sensitivity of the lower, dye-free emulsion layer is set so that under its influence the middle part of the curve The color of flowers is grown and becomes linear. The optical sensitization of the three interconnected layers is preferably in the same spectral region. However, it is not necessary to use the same optical sensitizer in all three layers. Thus, for example, the maximum of optical sensitization may be ADVANCED by several meters, or the sensitization maxima may be deduced from each other. Additional sensitivity in other regions of the spectrum can be achieved using other known masking effects. In the event that everything, the three layers are xenobiized in the area in which the dye forming the image is absorbed, l of the lower layer that does not contain dye can achieve extremely high sensitivity and (or) this layer can be sensitized to shorter wavelengths or, preferably, longer wavelengths (compared to the absorption maximum of the dye forming the image). Emulsion layers that do not contain azo dyes may contain a filter dye, in the presence of which, during exposure, there is a slight decrease in spectral permeability and (or) an increase in m ---. filter image sharpness. Such a dye is completely destroyed or washed away during processing. When using a material containing at least two halogen-silver emulsion layers having dyes, both dyes forming a color image are different from each other. Three layers can be used. In a three-layer material, the layers can be separated from each other by intermediate layers, and they, in turn, can contain common additives, such as filter dyes, substances that absorb in the ultraviolet region of the spectrum, or oxidizing agents. In multilayer systems, each dye-containing emulsion layer is provided with a dye-free emulsion layer located directly below it and directly above the ncm, so that the colored emulsion layers are separated from each other by two unstained and possibly between them intermediate layers. . Pyrazines, chinonsalips or phenazines are recommended as a catalyst for bleaching dyes. The catalysts may be in a photographic bath used for processing, or they may be present in any of the layers of the phosphorus membrane. Materials with a color density from 2.4 to 2.8 are used as a photographic transparent material. Example 1. A photographic material is obtained with the following arrangement of layers: 1) a dye-free emulsion layer; 2) a dye-containing emulsion layer; 3) a dye-free emulsion layer. The substrate is transparent. A bromide-silver emulsion with an iodine content of 1.5%, 53 g of silver per kg, and 70 g of gelatin per kg is used to make all three layers. Two dyes containing no dye, have as an optical sensitizer 3 mg / kg of the compound of the formula I ® / L-snn. In the emulsion layer containing the dye, 6.5 mg / kg of the compound I and 13 mg are added as an optical sensitizer. / kg forming the image of the dye Formula II

lN

-isVl

X / - G

 - {JbN N- / 7,

 NM,

The sensitizer of the formula I has a maximum sensitization at 760 them, the dye of the formula P has an absorption maximum at 650 them.

Stabilizers, wetting agents, plasticizers and tanning agents are introduced into the emulsion.

Emulsions are applied to a transparent substrate, as well as:

I. Layer 2 (for comparison);

II. Layer 3, Layer 2 and Layer. one.

All layers are iolated with 1.5 g / cm silver.

The material is exposed to a “gray wedge. M with an infrared filter and treated at 24 ° C and the developer for 6 minutes with the following composition, g:

p-Methylaminophenol sulfate2

Anhydrous sodium sulfite 50

Hydroquinone6

Anhydrous carbonate sodium 20

Potassium bromide2

Wadado 1000 ml

A stop-fixing solution (2 min) contains, g: Crystalline sodium thiosulfate 200 Anhydrous sodium sulfite 15

Sodium acetate (WNGO) 25

Acetic acid ice13 ml

Water Up to 1000 ml

Washed with water for 4 minutes

Dye Whitening Bath

(20 missions.), Ml:

Water500

Sulfuric acid (96%) 14

Crystalline sodium phosphate 1 g. Potassium iodide 20 g

6-Benzoylamino-2,3-dimethylquinoxalin 30 g

lil4 SO

CjHs1

c, n,

The results are shown in Table. 1. The smaller the value of the relative sensitivity of log E, the higher the sensitivity.

Table 1

From the above data it follows that irrigation II has a greater sensitivity and a flatter gradation curve than irrigation I.

Example 2. It is carried out analogously to Example 1, but 2.3 kg / kg of a sensitizer of formula III is introduced into layer 2 containing a dye.

© s

/ b CH — CH CH — CH CH — CH CH-l5.

Js

N

CjHij

This optical sensitizer has a maximum sensitization at 800 and 825. The three-layer system has a broad sensitization interval with two maxima at 760 MMC and 800-825. Material I is used for comparison to obtain Table 2 Water To 1000 ml Wash with water for 2 minutes. Silver bath (6 min) contains, ml: Water 500 Sulfuric acid (96%) 27 Crystal sulfate copper 20 g Potassium bromide 60 g Water Up to 1000 Washed with water for 2 minutes Fixing bath 4 min. The composition is the same as that of the remaining hot water bath. Two samples of colored indies are obtained, the evaluation of which is carried out by means of a color filter. WEH as in example 1. Both materials are exposed and processed. The results are shown in Table. 2. Material II has a much higher sensitivity and a gentler gradation curve than material L Example 3. Layer placement is the same as in Example 1. For all three layers, a silver-bromide emulsion with 4% iodide content is used. 53 g of silver and 70 g of gelatin for 1 "g. 16 mg / kg of the sensitizer of formula IV are introduced into the two layers of the dye-free emulsion. The lower the relative sensitivity log E, the greater the sensitivity. Example 4. It is carried out as in Example 3. However, the slate is poured with nanoscale 1.0 g / m silver on a white substrate. Both materials are exhibited, processed and scored. The results are shown in Table. 4. Table 4

, Hj s

I H I

C. / 1 s - sn: - s-sn - with

d) NO) N

Y

80 mg / kg of a sensitizer of formula IV and 15 g / kg of an image forming dye of formula V are introduced into the layer of the emulsion containing the dye.

1ЧНСО

The sensitizer of formula IV has a sensitization maximum of 640 nm, the dye of formula V has an absorption maximum at 535 nm.

On a transparent substrate containing 1.5 g / m2 of silver, are obtained as described in example 1, two materials I and II.

They are exposed to a “gray wedge using a red filter and treated as in example 1.

Two counter cones of material I and II are obtained, which are evaluated for a green light filter.

The measurement results are shown in Table. 3

Table 3

Example 1. The material of the following structure is obtained.

The protective layer, the emulsion layer containing the yellow dye sensitive to green light, the intermediate layer, the emulsion layer containing the purple dye sensitive to red light, the intermediate layer, the emulsion layer containing no dye that is sensitive to infrared rays, the emulsion layer containing an infrared sensitive dye, a dye-free emulsion layer that is infrared sensitive. transparent substrate (color density is about 2.6).

Three layers sensitized to infrared rays correspond to the layers described in Example 2.

Intermediate layers and protective layer contain gelatin in the amount of 2 g / m.

The emulsion layer with a purple nylon 0 contains 80 mg / kg of an optical sensitizer of formula IV, and as a dye forming an image, 15 g / kg of the compound of formula V.

The yellow dye emulsion layer contains 100 kg / kg of an optical sensitizer of formula VI and 15.4 g / kg of the dye forming the image of formula VII

50

CGH;

DOS

50-5

sn.

so.

H, cq

so;

CONKCH, V v, i

VII

SOs A sensitizer of formula VI has a sensitization maximum of 550 nm. The dye of formula VII has an absorption maximum at 416 im. All layers of the emulsion are watered with anos 1.5 g / m silver. Exposure to sunlight with aperture 8 is 1/250 sec. Due to the absorption of blue rays by a layer containing a yellow dye, the use of a yellow filter may be necessary only in special cases. Example 6. Conducted as in Example 1 for material II. An additional 3 mg / kg of a dye whitening catalyst of formula Vin N4 is added to the emulsion layer containing the dye. The material is exposed in Example 1 and treated in the same way, because the dye whitening bath does not contain a catalyst. On the developed color wedge, the same results are obtained as for material P of Example 1. Example 7. Material A is prepared as follows. A protective layer, an emulsion layer containing a turquoise dye sensitive to blue light, an intermediate layer, an emulsion layer containing a yellow dye sensitive to green light, an intermediate layer, a dye-free emulsion layer sensitive to red light are successively applied to the transparent substrate. , a red dye-sensitive emulsion layer containing a red light; a dye-free emulsion layer that is sensitive to red light. Three red-sensitized layers correspond to the layers described in Example 3. Intermediate layers and a protective layer are layers of 2 g gelatin per 2 m. In an emulsion layer containing a yellow dye, an optical sensitizer of 100 mg / kg of the formula (VI ) 1 And 20.5 g / kg dye, forming a color image of the formula VII given in example 5. These layers of the emulsion are poured over with the sediment 1 g / m silver. The blue dye emulsion layer, characterized by the intrinsic spectral sensitivity of the emulsion, contains 9 g / kg dye, which forms a color image of formula IX with an absorption maximum at 600 nm. This layer of esulsion is watered with sediment of 1.2 g / .m of silver. The survey was made with an exposure meter of 25 AA. Contact printing material B is prepared as follows. A protective layer, an emulsion layer containing a magenta dye sensitive to blue light, an intermediate layer, an emulsion layer containing a yellow dye sensitive to red light, an intermediate layer, a dye-free emulsion layer sensitive to green light are successively applied to the transparent substrate. , a layer of an emulsion containing a blue-green dye sensitive to green light, a layer of an emulsion containing no dye sensitive to green light. All three layers sensitive to green light consist of the emulsion shown in Example 3. The two layers of the dye-free emulsion contain 60 mg / kg optical sensitizer of the compound of formula VI of Example 5. The emulsion layer with blue-green dye contains 100 mg / kg optical sensitizer of formula VI of example 5, 13 g / kg of dye forming a color image of formula II given in example 1. For the manufacture of layers of emulsion with yellow and purple dye, iodide-silver-emulsion is used with an iodide content of 1.5%, 53 g / kg silver ra, 70 g / kg gelatin, which has a lower sensitivity than the three layers that are sensitive to green light. The emulsion layer with the yellow dye contains 80 mg / kg of the optical sensitizer described in example 3 of formula IV, and 15.4 g / kg of the dye forming the color image is given in example 5 of formula VII. An emulsion layer with a purple dye characterized by its own spectral sensitivity. The first emulsion contains 15 g / kg of the dye forming the color image given in example 3 of formula V. When using the second material B, the sensitivity of which corresponds to the sensitivity of the photographic positive material, you can get natural color prints of the material described above The visual density of the unexposed portions of the material for imprints corresponds to 2.6 density units. The subject of the invention. A method of obtaining a color photographic image of bleaching (silver dye using photographic material containing a substrate and at least one halogen-silver emulsion layer with a non-diffusing azo resin, ecoponated, developing and processing the material in the presence of a bleaching catalyst, characterized in that increase the photosensitivity, improve the gradation of the layers and color separation of the photographic material; a halo is placed under the emulsion layer from the MI azo dye and above it a generic emulsion layer that does not contain a dye of the same or higher sensitivity as the azo dye layer.