DE19912159A1 - Color photographic material, e.g. color negative film, has blue-sensitive tabular silver halide emulsion containing more emulsion stabilizer than red- and green-sensitive emulsions - Google Patents

Abstract

Color photographic material, e.g. color negative film, has blue-sensitive tabular silver halide emulsion containing more emulsion stabilizer than red- and green-sensitive emulsions. In color photographic material with blue- (BS), green- and red-sensitive silver halide (AgX) emulsion coat(s) containing yellow, magenta and cyan coupler(s) on a base, in which tabular AgX crystals with an aspect ratio >= 5 form >= 50% of the projected area of AgX crystals in BS layer(s), each emulsion contains emulsion stabilizer(s) (I) and the total amount of (I) in the BS emulsions is >= 30% greater than that in the other emulsions with respect to AgX.

Description

The invention relates to a color photographic material with a support, at least a blue-sensitive silver halo containing at least one yellow coupler gene emulsion layer, at least one red-sensitive, at least one blue green halide containing silver halide emulsion layer and at least one green-sensitive silver halide containing at least one magenta coupler emulsion layer contained in at least one of the blue sensitive silver halide emulsion layers of tabular silver halide crystals with an aspect ratio of at least 5 containing at least 50% of the projection area of the silver halo Identify genid crystals in the layer concerned.

As an aspect ratio of a tabular silver halide crystal, Ver ratio of the diameter of the circle with the same area to the thickness of the crystal stood.

From Research Disclosure 37 254 (1995). 5 288 ff are known compounds that one can add photographic emulsions for stabilization.

Further connections are in RD 308 119 (1989), Chapter VI, as well as in RD 36 544 (1994), Chapter VII. The stabilizers can the silver halide emulsions are added before, during or after their ripening.

To photographic images of high image quality regardless of the type of used Processing chemicals and the condition of the processing baths, The sensitometry of a photographic material must be robust against changes in the Processing conditions. This is with the state of the art materials Technology is not satisfactorily guaranteed, especially if the Materials tabular silver halide crystals in a blue sensitive layer  contain. Fluctuations in processing then result in e.g. B. col engaging pictures.

The invention has for its object in the color photographic materials, the tabular silver halide crystals for reasons of sensitivity and sharpness contained in a blue-sensitive layer to ver the processing stability improve.

This object is surprisingly achieved in that the silver halide emulsions of the material mentioned in the introduction at least one emulsion stabilizer included, with the total amount of emulsion stabilizer in the blue sensitive emulsions is at least 30 mol% larger than in the red or green-sensitive emulsions, each based on the same amount of silver halide.

Emulsion stabilizers in the sense of the invention are compounds which are inherent properties of the emulsion, such as sensitivity, fog and granularity, against external Influences, e.g. fluctuations in processing conditions, stabilize and have no -SM groups, where M is a hydrogen, a means monovalent metal atom or ammonium.

Suitable stabilizers are listed below:

wherein
R ¹ and R ² independently of one another H, alkyl, halogen, acyl, alkylthio, carboxy or alkoxycarbonyl and
R ^{3 is} H or halogen.

examples are

The photographic material preferably contains at least two blue-sensitive, at least two green sensitive and at least two red sensitive silver halide emulsion layers, the layers having the same color sensitivity differ in their photographic sensitivity.

The at least one blue-sensitive layer preferably contains at least one AgBrClI or AgBrI emulsion with 2 to 15 mol% AgI and at most 10 mol% AgCl.

The tabular silver halide crystals preferably make up at least 70% of the Projection surface of the emulsion in question and preferably have an aspect ver Ratio (AV) from 8 to 30. The grain size of the tabular silver emulsion halide crystals should be as uniform as possible; a volume is preferred variation coefficient (VVK) of at most 30%.

The tabular silver halide crystal emulsions are just like that other emulsions, additionally preferably matured and / or tellurium.  

The emulsion stabilizers are used in an amount of 0.1 to 20 mmol / mol silver halide of the layer in question, preferably 1 to 10 mmol / mol silver halide used.

The addition of the emulsion stabilizers to the silver halide emulsion can be used for any Time during the preparation of the emulsion: during the precipitation, during or after chemical ripening as well as during the manufacture of the cast solution.

The emulsions are prepared by customary processes; the emulsions stabilizers are known.

The material according to the invention is particularly characterized in that the filter differences (Dkop values) are largely independent of the processing conditions. The filter differences are the density differences between the density measured behind the blue and the green filter (D _BG ) and the density measured behind the red and the green filter (D _RG ). Changes in these filter differences due to the processing conditions lead to color-untrue prints and must therefore be as small as possible.

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 silver color bleaching process.

The photographic materials consist of a support on which at least one photosensitive silver halide emulsion layer is applied. Own as carrier especially thin films and foils. An overview of carrier material lien and auxiliary layers applied to the front and back are in Research Disclosure 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 emulsions layer and, if necessary, 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, cyan-coupling silver halide emulsion layers, 2 or 3 green-sensitive, purple-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 sub-layers generally being closer to the support than the more sensitive sub-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 out effects on 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 described.

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

Deviations in the number and arrangement of the photosensitive layers can occur to achieve certain results. For example, you can all highly sensitive layers in one layer package and all low-sensitivity layers layers into another layer package in a photographic film be set to increase 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 and spectral sensitization including suitable spectral sensi Bilisators can be found in 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 Sil berbromide iodide emulsions, which may also contain small amounts of silver chloride can contain. 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 XB (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 with the developer oxidation product release compounds that are photographic are effective, 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 ge in high-boiling organic solvents dissolves or disperses. These solutions or dispersions are then in one emulsified aqueous binder solution (usually gelatin solution) and lie after drying the layers as fine droplets (0.05 to 0.8 µm through knife) in the layers.

Suitable high-boiling organic solvents, methods for incorporation into the Layers of photographic material and other methods, chemical ver Finding bonds in 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 an undesirable diffusion of developer oxidation products from a light sensitive to another light-sensitive layer with different spectra Prevent central sensitization.  

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.

The photographic material can also UV-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, anti-oxidants, D _Min dyes, additives to improve dye, coupler and white stability and to reduce the color fog, plasticizers (latices) biocides 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, XI and XIII (1995), P. 84 ff and in Research Disclosure 38957, Parts VI, VIII, IX and X (1996), p. 607 and 610 ff

The layers of color photographic materials are typically hardened, i.e. that is Binder used, preferably gelatin, is replaced by suitable chemical Process 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), Pp. 95 ff and in Research Disclosure 38957, parts XVIII, XIX and XX (1996), P. 630 ff published together with exemplary materials.  

In the following examples, the silver described in Table 1 halide emulsions used.

Table 1

Overview of the AgBrI emulsions

example 1

A color photographic recording material for color negative color development was produced (layer structure 1A) 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; the silver halides are stabilized with 1 mmol ST-1 per mol AgNO ₃ . All emulsions are chemically ripened with sulfur, selenium and gold.

1st layer (antihalo layer)

0.3 g black colloidal silver
1.2 g gelatin
0.3 g UV absorber UV-1
0.2 g EOP (developer oxidation product) scavenger SC-1
0.02 g tricresyl phosphate (CPM)

2nd layer (low red sensitive layer)

0.7 g AgNO ₃

a spectrally red-sensitized AgBrI emulsion, 4 mol% iodide, average grain diameter 0.42 µm, AV 5, VVK 25%
1 g gelatin
0.35 g of colorless coupler C-1
0.05 g colored RC-1 coupler
0.03 g colored coupler YC-1
0.36 g CPM

3rd layer (medium red sensitive layer)

0.8 g AgNO ₃

a spectrally red-sensitized AgBrI emulsion, 5 mol% iodide, average grain diameter 0.53 µm, AV 6, VVK 23%
0.6 g gelatin
0.15 g of colorless coupler C-2
0.03 g colored RC-1 coupler
0.02 g DIR coupler D-1
0.18 g CPM

4th layer (highly red-sensitive layer)

1 g AgNO ₃

a spectrally red-sensitized AgBrI emulsion, 6 mol% iodide, average grain diameter 0.85 µm, AV 9, pre-sale 20%
1 g gelatin
0.1 g colorless coupler C-2
0.005 g DIR coupler D-2
0.11 g CPM

5th layer (intermediate layer)

0.8 g gelatin
0.07 g EOP catcher SC-2
0.06 g of aluminum salt of aurintricarboxylic acid

6th layer (low green sensitive layer)

0.7 g AgNO ₃

a spectrally green-sensitive AgBrI emulsion, 4 mol% iodide, average grain diameter 0.35 µm, AV 5, pre-sale 20%
0.8 g gelatin
0.22 g of colorless coupler M-1
0.065 g colored coupler YM-1
0.02 g DIR coupler D-3
0.2 g CPM

7th layer (medium green sensitive layer)

0.9 g AgNO ₃

a spectrally green-sensitive AgBrI emulsion, 4 mol% iodide, average grain diameter 0.50 µm, AV 7, pre-sale 24%
1 g gelatin
0.16 g of colorless coupler M-1
0.04 g colored coupler YM-1
0.015 g DIR coupler D-4
0.14 g CPM

8th layer (highly green-sensitive layer)

0.6 g AgNO ₃

a spectrally green-sensitized AgBrI emulsion, 6 mol% iodide, average grain diameter 0.70 µm, AV 10, pre-sale 20%
1.1 g gelatin
0.05 g colorless coupler M-2
0.01 g colored coupler YM-2
0.02 g DIR coupler D-5
0.08 g CPM

9th layer (yellow filter layer)

0.09 g yellow dye GF-1
1 g gelatin
0.08 g EOP catcher SC-2
0.26 g CPM

10th layer (low blue-sensitive layer)

0.3 g AgNO ₃

a spectrally blue-sensitized AgBrI emulsion, 6 mol% iodide, average grain diameter 0.44 µm, AV 4, pre-sale 20%
0.5 g AgNO ₃

a spectrally blue-sensitized AgBrI emulsion, 6 mol% iodide, average grain diameter 0.50 µm, AV 5, VVK18%
1.9 g gelatin
1.1 g of colorless coupler Y-1
0.037 g DIR coupler D-6
0.6 g CPM

11th layer (highly blue-sensitive layer)

0.6 g AgNO ₃

a spectrally blue-sensitized AgBrI emulsion, 7 mol% iodide, average grain diameter 0.95 µm
1.2 g gelatin
0.1 g colorless coupler Y-1
0.006 g DIR coupler D-7
0.11 g CPM

12th layer (Mikrat layer)

0.1 g AgNO ₃

a Mikrat-AgBrI emulsion, 0.5 mol% iodide, average grain diameter 0.06 µm
1 g gelatin
0.004 mg K ₂

[PdCl ₄

]
0.4 g UV absorber UV-2
0.3 g CPM

13th layer (protective and hardening layer)

0.25 g gelatin
0.75 g of H-1 curing agent

The total layer structure had a swelling factor ≦ 3.5 after curing.

Substances used in example 1:

After exposure of a gray wedge, the development according to "The British Journal of Photography ", 1974, pages 597 and 598. The developer solution according to table 2 varies:

Table 2

In the layer structures 1A to 1N, the layers are of different amounts of the stabilizer ST-1 added. The changes in the layer structures are in Table 3 reproduced. The amounts of ST-1 given in the table are in the respective layers to the standard amount of 1.0 mmol Add ST-1 per mole of silver halide.

Table 3

Table 4 shows the changes in the filter differences depending on the developer solution used. The filter differences are the density differences between the density measured behind the blue and the green filter (ΔD _BG ) and between the density measured behind the red and the green filter (ΔD _RG ) with an exposure of 0.8 log E above the sensitivity point Green, which is defined by a purple density of 0.15 over veil. Since the processing should have as little influence as possible on the filter differences, small changes in the filter differences are advantageous. This is best achieved with the material according to the invention.

Table 4

As can be seen, the materials according to the invention have an improved Ver ratio of sensitivity to processing stability.

Example 2

The layer structures 2A to 2D were produced in exactly the same way as in Example 1 described, however, the emulsions and the amounts of stabilizer were noisy Table 5 used. The amounts of ST-1 given in the table are in the respective layers to the standard amount of 1.0 mmol ST-1 per mole of silver halide.

Table 5

Table 6 shows the changes in the filter differences depending on the developer solution used.  

Table 6

As can be seen, the materials according to the invention have an improved Ver ratio of sensitivity to processing stability.

Example 3

The layer structures 3A to 3D were produced in exactly the same way as in Example 1 wrote, but the stabilizers were listed in Table 7 in the given amounts used. The quantities indicated in the table Stabilizers are added in the respective layers to the standard ones Add 1.0 mmol of ST-1 per mol of silver halide.  

Table 7

Table 8 shows the changes in the filter differences depending on the developer solution used.

Table 8

As can be seen, the materials according to the invention have a very good ratio from sensitivity to processing stability.

Claims (8)

1. Color photographic material with a support, at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler and at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler which is present in at least one of the blue-sensitive silver halide emulsion layers contains crystals with an aspect ratio of at least 5, which make up at least 50% of the projection area of the silver halide crystals of the layer in question, characterized in that the silver halide emulsions each contain at least one emulsion stabilizer, the total amount of emulsion stabilizer in the blue-sensitive emulsions being at least 30 mol% is larger than in the red or green sensitive emulsions, based in each case on the same Amount of silver halide. 2. Color photographic material according to claim 1, characterized in that the emulsion stabilizer has no SM groups, where M is a Is hydrogen, monovalent metal cation or ammonium. 3. Color photographic material according to claim 1, characterized in that it at least two blue sensitive, at least two green sensitive and contains at least two red-sensitive silver halide emulsions, wherein the layers of the same color sensitivity in their photographic Differentiate sensitivity. 4. Color photographic material according to claim 1, characterized in that the at least one blue-sensitive layer at least one AgBrClI or  AgBrI emulsion with 2 to 15 mol% AgI and at most 10 mol% AgCl contains. 5. Color photographic silver halide material according to claim 1, characterized characterized in that the tabular silver halide crystals of at least a blue sensitive layer at least 70% of the projection area of the Identify silver halide crystals of the relevant layer and one Have aspect ratio of 8 to 30. 6. Color photographic silver halide material according to claim 1, characterized characterized in that the emulsion with the tabular silver halide crystals is selenium and / or tellurium matured. 7. Color photographic silver halide material according to claim 1, characterized characterized in that the emulsion stabilizers in an amount of 0.1 to 20 mmol / mol of silver halide of the layer in question are used. 8. Color photographic silver halide material according to claim 1, characterized in that the emulsion stabilizer of the formula
owns.