DE19800836A1 - Color photographic material with increased blue and green speed - Google Patents

Abstract

In color photographic material with red-, green- and blue-sensitive silver halide emulsion layer(s) containing complementary couplers, a cyanine dye with specified absorption maximum is added to at least one blue-sensitive and at least one green-sensitive emulsion layer. In color photographic material with red, green and blue-sensitive silver halide emulsion layer(s) containing cyan, magenta and yellow coupler respectively and optionally other light-insensitive layers on a base, a cyanine dye is added to at least one blue-sensitive and at least one green-sensitive emulsion layer, in addition to the usual sensitizing dyes. The absorption maximum in methanol solution is in the 428-500 nm range for each added cyanine dye and the difference between the absorption maxima for the cyanine dyes added to the blue- and green-sensitive emulsions is not more than 70 nm.

Description

Usually in color photographic silver halide materials for the spec central sensitization of the blue, green and red spectral range struk turell different dyes used.

Efforts have not been lacking in the well-known color photographic record materials with regard to their spectral sensitivity and their color rendering to improve. EP 409 019 describes a color photographic recording material described improved color rendering, which is achieved in that both green sensitive as well as red sensitive silver halide emulsion layers by using one or more so-called gap sensitization dyes an additional sensitization for light from the gap between the be neighboring main spectral ranges green and red. As a result, the be neighboring spectral sensitivity curves in the area of secondary spectral sensitivity Lichity (gap) increased so that a maximum of 0.6 logarithmic exposure units in the area of sub-spectral sensitivity more are required to be the same Color density as in the area of the neighboring main spectral sensitivities testify.

It has now been found that not only the color rendering, but also the Emp sensitivity can be improved if one or more cyanine dyes with be agreed spectral absorption properties for both sensitization in the green spectral range as well as for sensitization in the blue spectral range will be used.

The invention relates to a color photographic recording material with a Layer support and arranged thereon at least one red-sensitive silver halo gene emulsion layer with at least one cyan coupler, at least one green sensitive silver halide emulsion layer with at least one magenta coupler, at least one blue-sensitive silver halide emulsion layer with at least a yellow coupler and possibly other non-light-sensitive layers,  characterized in that at least one of its blue-sensitive silver halo gene emulsion layers and at least one of its green sensitive silver halo gene emulsion layers additionally contain at least one cyanine dye each in methanolic solution an absorption maximum in the range of 428-500 nm, preferably in the range of 443-470 nm, the absorption maximum of additional cyanine dye in the blue sensitive silver halide emulsion layer and the absorption maximum of the additional cyanine dye in the green sensitive layer, each measured in methanolic solution, by no more than 70 nm and particularly preferably not more than 50 nm apart.

The additional cyanine dyes mentioned are preferably Cyanines that have at least one of the (two) ring nitrogen atoms with one Acid-substituted alkyl group. Particularly suitable examples of these Cyanine dyes belong to the class of benzimidazole cyanines or the substance class of the Oxathiacyanine.

In a preferred embodiment of the invention, the additional cyanine color substance in the blue-sensitive silver halide emulsion layer identical to that for additional cyanine dye in the green-sensitive silver halide emulsion layer. Cyanine dyes are regarded as "identical" in this regard match the dye chromophore, even if the La the existing counterions do not match.

Some cyanine dyes suitable according to the invention are given below by way of example with the corresponding absorption maxima λ _max measured in methanolic solutions.

Examples of color photographic materials are color negative films, color reversal films, Color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process. An overview can be found in Research Disclosure 37038 (1995) and Research Disclosure 38957 (1996).

The photographic materials consist of a support on which at least one photosensitive silver halide emulsion layer is applied. Suitable as a carrier especially thin films and foils. An overview of substrates and auxiliary layers applied to their front and back is in Research Disclo sure 37254, part 1 (1995), p. 285 and in Research Disclosure 38957, part XV (1996), P. 627.  

The color photographic materials usually contain at least one red sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and optionally intermediate layers and protective layers.

Depending on the type of photographic material, these layers can be arranged differently. This is shown for the most important products:
Color photographic films such as color negative films and color reversal films have 2 or 3 red-sensitive, blue-green coupling silver halide emulsion layers, 2 or 3 green-sensitive, purely coupling silver halide emulsion layers and 2 or 3 blue-sensitive, yellow coupling silver halide emulsion layers on the support in the order given below. The layers of the same spectral sensitivity differ in their photographic sensitivity, with the less sensitive partial layers generally being arranged closer to the support than the higher sensitive partial layers.

Between the green sensitive and blue sensitive layers is common a yellow filter layer is applied, which prevents blue light from lying in the below layers.

The possibilities of the different layer arrangements and their effects the photographic properties are described in J. Inf. Rec. Mats., 1994, Vol. 22, Pages 183-193 and in Research Disclosure 38957 Part XI (1996), p. 624 ben.

Color photographic paper, which is usually much less sensitive to light than a color photographic film shows in the order given below the wearer usually has a blue-sensitive, yellow-coupling silver halide nidemulsion layer, a green-sensitive, purple-coupling silver halide emulsion sion layer and a red-sensitive, cyan-coupling silver halide emulsion layer on; the yellow filter layer can be omitted.  

Deviations in the number and arrangement of the light-sensitive layers can lead to Achieve certain results. For example, everyone highly sensitive layers in a layer package and all low-sensitive layers Layers combined to form another layer package in a photographic film be summarized to increase the sensitivity (DE-25 30 645).

Essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers.

Information on suitable binders can be found in Research Disclosure 37254, Part 2 (1995), p. 286 and in Research Disclosure 38957, Part II.A (1996), p. 598.

Information about suitable silver halide emulsions, their preparation, maturation, stabilization lization and spectral sensitization including suitable spectral sensitization For more information, see Research Disclosure 37254, Part 3 (1995), p. 286, in Research Disclosure 37038, Part XV (1995), p. 89 and in Research Disclosure 38957, Part V.A. (1996), p. 603.

Photographic materials with camera sensitivity usually contain silver bromide iodide emulsions, which may also contain small amounts of silver chloride can. Photographic copying materials contain either silver chloride bromide emulsions with up to 80 mol% AgBr or silver chloride bromide emulsions with over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288, in Research Disclosure 37038, Part II (1995), p. 80 and in Research Disclosure 38957, Part X.B (1996), p. 616. The maximum absorption of the dyes formed from the couplers and the color developer oxidation product is preferably in the following ranges: yellow coupler 430 to 460 nm, purple couplers 540 to 560 nm, cyan couplers 630 to 700 nm.  

In color photographic films, to improve sensitivity, grainy speed, sharpness and color separation are often used in the compounds involved in the reaction release compounds with the developer oxidation product that have a photographic effect are sam, e.g. B. DIR couplers that release a development inhibitor.

Information on such compounds, in particular couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290, in Research Disclosure 37038, Part XIV (1995), p. 86 and in Research Disclosure 38957, Part X.C (1996), p. 618.

The mostly hydrophobic color coupler, but also other hydrophobic components of the Layers are usually dissolved in high-boiling organic solvents or dispersed. These solutions or dispersions are then in an aqueous Binder solution (usually gelatin solution) emulsified and lie after Drying the layers as fine droplets (0.05 to 0.8 µm diameter) in the Layers before.

Suitable high-boiling organic solvents, methods for incorporation into the Layers of photographic material and other methods, chemical compound Introducing solutions into photographic layers can be found in Research Disclosure 37254, Part 6 (1995), p. 292.

The usually indicated between layers of different spectral sensitivity ordered non-photosensitive interlayers may contain agents that have a unwanted diffusion of developer oxidation products from a photosensitive in a different light-sensitive layer with different spectral sensitivity prevent bilization.

Suitable connections (white coupler, scavenger or EOP catcher) can be found in Research Disclosure 37254, Part 7 (1995), p. 292, in Research Disclosure 37038, Part III (1995), p. 84 and in Research Disclosure 38957, Part X.D (1996), p. 621 ff.  

The photographic material can also UV-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, anti-oxidants, D _Min dyes, plasticizers (latices), biocides and additives to improve the coupler and dye stability, to reduce the color fog and to reduce yellowing and other included. Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), p. 292, in Research Disclosure 37038, Parts IV, V, VI, VII, X, M and XIII (1995), p. 84 ff and in Research Disclosure 38957, Parts VI, VIII, IX and X (1996), pp. 607 and 610 ff.

The layers of color photographic materials are typically hardened, i.e. that is binder used, preferably gelatin, is by suitable chemical Ver networked.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), P. 294, in Research Disclosure 37038, Part XII (1995), p. 86 and in Research Disclosure 38957, Part II.B (1996), p. 599.

After photographic exposure, color photographic materials become their character processed according to different processes. Details on ver procedures and chemicals required for this are in Research Disclosure 37254, Part 10 (1995), p. 294, in Research Disclosure 37038, parts XVI to XXIII (1995), p. 95 ff and in Research Disclosure 38957, parts XVIII, XIX and XX (1996), p. 630 ff published together with exemplary materials.

example 1

A color photographic recording material for color negative color development was produced (layer structure 1A - comparison) by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m ² . The corresponding amounts of AgNO _{3 are} given for the silver halide application. All silver halide emulsions per 100 g of AgNO _{3 were} stabilized with 0.1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Layer structure 1A

Layer 1: (antihalo layer)
black colloidal silver sol with
0.3 g Ag
1.2 g gelatin
0.4 g UV absorber UV-1
0.02 g tricresyl phosphate (CPM)

Layer 2: (intermediate layer)
1.0 g gelatin

Layer 3: (1st red-sensitized layer, slightly sensitive)
Red-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.5 µm; spectrally sensitized with the sensitizing dyes RS-1, RS-2 and RS-3 in a ratio of 1: 3: 0.5) from 2.7 g AgNO ₃ , With
2.0 g gelatin
0.88 g cyan coupler C-1
0.05 g colored coupler CR-1
0.07 g colored coupler CY-1
0.02 g DIR coupler DIR-1
0.75 g CPM

Layer 4: (2nd red-sensitized layer, highly sensitive)
Red-sensitized silver bromide iodide emulsion (12 mol% iodide; average grain diameter 1.0 µm; spectrally sensitized with the sensitizing dyes RS-1, RS-2 and RS-3 in a ratio of 1: 3.1: 0.3) from 2.2 g AgNO ₃ , with
1.8 g gelatin
0.19 g of cyan coupler C-2
0.17 g CPM

Layer 5: (intermediate layer)
0.4 g gelatin
0.15 g white coupler W-1
0.06 g of aluminum salt of aurintricarboxylic acid

Layer 6: (1st green-sensitized layer, slightly sensitive)
Green-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.35 µm; spectrally sensitized with the sensitizing dyes GS-1, GS-2 and GS-3 in a ratio of 2.8: 1: 0.2) from 1.9 g AgNO ₃ , with
1.8 g gelatin
0.54 g purple coupler M-1
0.065 g colored coupler MY-1
0.24 g DIR coupler DIR-1
0.6 g CPM

Layer 7: (2nd green sensitive layer, highly sensitive)
green-sensitized silver bromide iodide emulsion (9 mol% iodide; average grain diameter 0.8 µm; spectrally sensitized with the sensitizing dyes GS-1, GS-2 and GS-3 in the ratio 2.8: 0.9: 0.25) from 1, 25 g AgNO ₃ , with
1.1 g gelatin
0.195 g purple coupler M-2
0.05 g colored coupler MY-2
0.245 g CPM

Layer 8: (yellow filter layer)
yellow colloidal silver sol with
0.09 g Ag
0.25 g gelatin
0.08 g Scavenger SC-1
0.40 g formaldehyde scavenger FF-1
0.08 g CPM

Layer 9: (1st blue-sensitive layer, slightly sensitive)
Blue-sensitized silver bromide iodide emulsion (6 mol% iodide; average grain diameter 0.6 µm; spectrally sensitized with the sensitizing dye BS-1) from 0.6 g AgNO ₃ , with
2.2 g gelatin
1.1 g yellow coupler Y-1
0.037 g DIR coupler DIR-1
1.14 g CPM

Layer 10: (2nd blue sensitive layer, highly sensitive)
Blue-sensitized silver bromide iodide emulsion (10 mol% iodide; mean grain diameter 1.2 µm; spectrally sensitized with the sensitizing dye BS-1) from 0.6 g AgNO ₃ , with
0.6 g gelatin
0.2 g yellow coupler Y-1
0.003 g DIR coupler DIR-1
0.22 g CPM

Layer 11: (micrate layer)
Mikrat-silver bromide iodide emulsion (0.5 mol% iodide; average grain diameter 0.06 µm) from 0.06 g AgNO ₃ , with

1.0 g gelatin
0.3 g UV absorber UV-2
0.3 g CPM

Layer 12: (protective and hardening layer)
0.25 g gelatin
0.75 g of curing agent H-1,
so that the total layer structure had a swelling factor of 3.5 after curing.

Compounds used in layer structure 1A:

Sensitizing dyes used in Example 1:

In the layer structures 1B, 1C, 1D, 1E and 1F according to the invention, the spec central sensitization changed as follows:  

Layer structure 1B

Layer structure 1C

Layer structure 1D

Layer structure 1E

Layer structure 1F

After exposing a gray wedge, the layer structures 1A to 1F were made a color negative process, which is published in "The British Journal of Photo graphy "1984, pages 597 and 598.

The sensitivities E _blue and E _{green of} the layer structures 1B to 1F according to the invention are compared in Table 1 to those of the comparison layer structure 1A.

Table 1

Claims (4)

1. Color photographic recording material with a layer support and arranged thereon at least one red-sensitive silver halide emulsion layer with a cyan coupler, at least one green-sensitive silver halide emulsion layer with a magenta coupler, at least one blue-sensitive silver halide emulsion layer with a yellow coupler and, if appropriate, further non-light-sensitive layers, characterized in that at least one of them blue-sensitive silver halide emulsion layers and at least one of its green-sensitive silver halide emulsion layers, in addition to the usual sensitizing dyes, each contain at least one cyanine dye, which has a maximum absorption in the range of 428-500 nm in methanolic solution, the absorption maximum of the additional cyanine dye in the blue-sensitive silver halide desorption maximum and the desorption layer additional cyanine dye in the green Indian silver halide emulsion layer, each measured in methanolic solution, not more than 70 nm apart. 2. Recording material according to claim 1, characterized in that the Absorption maximum of the additional cyanine dye in the blue sensitivity Lich silver halide emulsion layer and the absorption maximum of additional cyanine dye in the green sensitive silver halide emul sion layer, each measured in methanolic solution, by no more than 50 mm apart. 3. Recording material according to claim 1, characterized in that the to additional cyanine dye in the blue-sensitive silver halide emulsion layer is identical to the additional cyanine dye in the green sensitivity Liche silver halide emulsion layer.   4. Recording material according to claim 1, characterized in that the Absorption maximum is in the range from 443 to 470 nm.