DE19749589A1 - Photographic silver halide colour negative material - Google Patents

Abstract

Photographic silver halide (AgX) material has >= 2 AgX emulsion layers of different photographic speed for each of the 3 spectral regions blue, green and red. The novel features are that, in one of the 3 spectral regions, (a) the selective exposure 0.5 logarithmic (log) unit greater than that needed to give a density 0.2 above fog gives >= 0.1 higher density (density difference DELTA D<0.5>) in the negative in the complementary colour after processing than the white exposure 0.5 log unit greater than that giving a density 0.2 above fog; (b) the selective exposure 1.0 log unit greater than that needed to give a density 0.2 above fog gives a density difference ( DELTA D<1.0>) after processing \} twice DELTA D<0.5>; and (c) the selective exposure 1.5 log units greater than that needed to give a density 0.2 above fog gives a density difference ( DELTA D<1.5>) after processing \} 2.5 times DELTA D<0.5>.

Description

The invention relates to a photographic color negative material whose color is again with under- and overexposure is just as good as with correct Exposure.

Color negative films are characterized by a high tolerance to overexposure out. The color brilliance decreases with moderate overexposure from one to two Aperture levels too, whereas underexposure in addition to the expected Ver deterioration in tracing in the shadows also leads to a decrease in the Color brilliance leads. This phenomenon contributes to the loss of picture quality Underexposure, but is not a necessary consequence of underexposure.

The dependence of the color brilliance on the exposure occurs because the so-called called inter-image effect (IIE) generally increases with the negative density. IIE is the phenomenon that light of a certain spectral spectrum rich after processing gives a negative density that of that is different, which with simultaneous action of those parts of the spec is obtained that complement the spectral range to white light. He wishes is the occurrence of a higher density with selective exposure, what is called a positive IIE referred to as.

A known measure to achieve a positive IIE is to use it So-called DIR coupler, which when coupled with the oxidation product of Color developer a residue that inhibits further development, the inhibitor, split off. Because with white exposure, more inhibitor in the layer structure overall is generated than with selective exposure, a positive IIE arises.

A disadvantage of this method is that the density difference from selective exposure increases White exposure is usually proportional to the density since the amount of abge cleaved inhibitor with the amount of developer oxidation product and thus the Color density increases. As a result of this, the color brilliance increases denser, i.e. more exposed negatives.

The effectiveness of DIR couplers can be determined by using Emul sions affect the different speeds under otherwise identical conditions develop. The faster an emulsion develops, the less pronounced it is  Development inhibition by DIR couplers. Generally it is found that emulsions with higher iodide content are slower than those with lower develop.

Another measure to influence the IIE is the use of Mask couplers that are generally used to reduce the impact to compensate for the inevitable secondary densities of the image dyes produced. By using larger quantities of mask couplers than is required for this, however, a IIE can also be created.

For the color brilliance, the absolute density difference between white and selective crucial areas. Therefore it is enough for a good and illuminating independent color saturation, high at low negative densities Differences in density between the respective color density with selective exposure and set the appropriate color density for white exposure, but then too higher negative densities no longer increases sharply.

The invention has for its object to provide a color negative material that delivers brilliant colors even with scarce exposure and one has equally good color rendering that is not very dependent on the exposure.

It has now been found that this object can be achieved with a material which has at least two silver halide emulsion layers which differ in their photographic sensitivity for each of the three spectral ranges blue, green and red, characterized in that the layers are matched to one another in such a way that

• a) the 0.5 logarithmic units greater selective exposure in one of the three spectral ranges than is necessary to achieve a density of 0.2 via fog, after processing a density that is at least 0.1 higher (density difference ΔD ^0.5 ) in the negative in the complementary color than in the case of white exposure, which is also 0.5 logarithmic units larger than the white exposure, which produces a density of 0.2 above fog,
• b) the selective exposure greater by 1.0 logarithmic units in one of the three spectral ranges than is necessary to achieve a density of 0.2 via fog, after processing results in a density difference ΔD ^1.0 which is at most twice the density difference ΔD Is ^0.5 and
• c) the selective exposure greater by 1.5 logarithmic units in one of the three spectral ranges than is necessary to achieve a density of 0.2 via fog results in a density difference ΔD ^1.5 after processing which does not exceed the 2.5- times the density difference ΔD is ^0.5 .

The desired difference in density can be selected using specific methods Reach emulsions, DIR and mask couplers.

Preferably contains only the silver halide emulsion layer with the highest photographic sensitivity using a DIR coupler that is diffusible Inhibitor cleaves. In particular, the diffusibility is greater than 0.4.

The method for determining the diffusibility of the inhibitor is in EP-A 115,302.

Preferably, the silver halide emulsion layer contains the highest photo graphic sensitivity a silver halide emulsion, the proportion of AgI um is at least 4 mol% greater than the proportion of AgI of all emulsions in the Silver halide emulsion layers of the same color sensitivity, but less photographic sensitivity.

Both the green and the red sensitive emulsions are preferred layers configured in the manner according to the invention.

In a further preferred embodiment, each contains the highest sensitive layer of the green-sensitive spectral range and the red-sensitive a higher spectral range, based on the order to master couplers Application to mask couplers as the less sensitive sub-layers.

Preferably, the color photographic material of the invention is a color negative Movie.

Color negative films usually have the following series follow 2 or 3 red-sensitive, cyan-green domes on a transparent support  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. The layers of the same spectral sensitivity differ in their photographic sensitivity, the less sensitive sub-layers are usually arranged closer to the carrier are layers than the more sensitive part.

Between layers of different spectral sensitization are becoming more common wise intermediate layers provided that the diffusion of the developer oxidation product from a layer of a certain spectral sensitization into a Should prevent another spectral sensitization layer, otherwise color falsifications would result.

Such a film is usually between the green sensitive and Blue-sensitive layers have a yellow filter layer attached, which gives blue light prevents it from reaching the layers below.

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 to another layer package in a photographic film be summarized to increase the sensitivity (DE 25 30 645).

The possibilities of different layer arrangements and their effects The photographic properties are described in J. Inf. Rec. Mats., 1994, Vol. 22, pages 183 to 193.

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.

Information about suitable silver halide emulsions, their preparation, maturation, Stabilization and spectral sensitization including suitable spectrals sensitizers can be found in Research Disclosure 37254, Part 3 (1995), pp. 286 and in Research Disclosure 37038, Part XV (1995), p. 89.  

Color negative films usually contain silver bromide iodide emulsions may also contain small amounts of silver chloride.

Information on the color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288 and in Research Disclosure 37038, Part II (1995), p. 80. The maximum absorption of that from the couplers and the color developer oxide dyes formed product is preferably in the following areas: Yellow coupler 430 to 460 nm, purple coupler 540 to 560 nm, cyan coupler 630 up to 700 nm.

In color photography films, to improve sensitivity, Graininess, sharpness and color separation are often used in compounds Reaction with the developer oxidation product release compounds, the photo are graphically effective, e.g. B. DIR couplers that have a development inhibitor columns.

Information on such connections, in particular couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290 and in Research Disclosure 37038, Part XIV (1995), p. 86.

Mostly hydrophobic color couplers, but also other hydrophobic components of the layers, are usually in high-boiling organic solvents dissolved or dispersed. 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 a photographic material and other methods, chemical Introducing connections into photographic layers can be found in Research Disclosure 37254, Part 6 (1995), p. 292.

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

The photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, additives to improve the stability of dyes, couplers and whites as well as to reduce the color fog, plasticizers (latices), Contain biocides and others.

Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), P. 292 and in Research Disclosure 37038, parts IV, V, VI, VII, X, M and XIII (1995), p. 84 ff.

The layers of color photographic materials are typically hardened, i.e. H., the binder used, preferably gelatin, is by suitable cross-linked chemical processes.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294 and in Research Disclosure 37038, Part XII (1995), page 86.

After imagewise exposure, color photographic materials become their character ter processed according to different processes. Details of the Procedures and chemicals required for this are in Research Disclosure 37254, part 10 (1995), p. 294 and in Research Disclosure 37038, parts XVI to XXIII (1995), p. 95 ff. Published together with exemplary materials.

The yellow filter layer usually contains yellow colloidal silver or one yellow dye.

example 1

A color photographic recording material for color negative color development was prepared by applying the following layers in the order given to a transparent layer of cellulose tri acetate. The quantities given relate to 1 m ² . For the silver halide application, the corresponding amounts of AgNO ₃ are given; the silver halide is stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of AgNO ₃ .

1st layer (antihalo layer)

0.2 g black colloidal silver
1.4 g gelatin
0.4 g UV absorber UV 1
0.04 g tricresyl phosphate (CPM)

2nd layer (low red sensitive layer)

0.9 g AgNO ₃

a spectrally red-sensitized Ag (Br, I) emulsion with 6 mol% iodide, average grain diameter 0.55 µm
0.83 g gelatin
0.28 g of colorless coupler C-1
0.005 g DIR coupler D-1
0.015 g colored RC-1 coupler
0.017 g colored coupler YC-1
0.302 g CPM

3rd layer (medium red sensitive layer)

1.1 g AgNO ₃

a spectrally red-sensitized Ag (Br, I) emulsion with 5 mol% iodide, average grain diameter 0.70 µm
0.20 g coupler C-1
0.004 g DIR coupler D-1
0.026 g colored RC-1 coupler
0.018 g colored coupler YC-1
0.90 g gelatin
0.282 g CPM

4th layer (highly red-sensitive layer)

1.4 g AgNO ₃

a spectrally red-sensitized Ag (Br, I) emulsion, 8 mol% iodide, average grain diameter 1.10 µm
1.2 g gelatin
0.05 g of colorless coupler C-1
0.004 g DIR coupler D-2
0.01 g colored coupler RC-1
0.01 g colored coupler YC-1
0.06 g CPM

5th layer (intermediate layer)

0.72 g gelatin
0.04 g white coupler W-1

6th layer (low green sensitive layer)

0.5 g AgNO ₃

a spectrally green-sensitized Ag (Br, I) emulsion, 6 mol% iodide, average grain diameter 0.55 µm
0.95 g gelatin
0.31 g colorless coupler M-1
0.01 g DIR coupler D-1
0.012 g DIR coupler D-2
0.065 g colored coupler YM-1
0.03 g CPM

7th layer (medium green-sensitive layer)

1.2 g AgNO ₃

a spectrally green-sensitized Ag (Br, I) emulsion, 5 mol% iodide, mean grain diameter 0.70 µm,
0.24 g of colorless coupler M-1
0.024 g colored coupler YM-1
0.008 g colored coupler YM-2
0.014 g DIR coupler D-1
0.012 g DIR coupler D-2
0.74 g gelatin
0.046 g CPM

8th layer (highly green-sensitive layer)

1.4 g AgNO ₃

a spectrally green-sensitized Ag (Br, I) emulsion, 8 mol% iodide, average grain diameter 1.10 µm
0.75 g gelatin
0.06 g of colorless coupler M-1
0.013 g colored coupler YM-1
0.004 g colored coupler YM-2
0.005 g DIR coupler D-2
0.017 g CPM

9th layer (yellow filter layer)

0.06 g of yellow colloidal silver
0.75 g gelatin
0.04 g white coupler W-1

10th layer (low blue-sensitive layer)

0.55 g AgNO ₃

a spectrally blue-sensitized Ag (Br, I) emulsion, 7 mol% iodide, average grain diameter 0.65 µm
1.3 g gelatin
0.35 g of colorless coupler Y-1
0.005 g DIR coupler D-1
0.355 g CPM

11th layer (medium blue-sensitive layer)

0.55 g AgNO ₃

a spectrally blue-sensitized Ag (Br, I) emulsion, 7 mol% iodide, average grain diameter 0.80 µm
0.28 g of colorless coupler Y-1
0.008 g DIR coupler D-1
0.004 g DIR coupler D-2
0.65 g gelatin
0.288 g CPM

12th layer (highly blue-sensitive layer)

1.1 g AgNO ₃

a spectrally blue-sensitized Ag (Br, I) emulsion, 9 mol% iodide, average grain diameter 1.25 µm,
0.85 g gelatin
0.16 g of colorless coupler Y-1
0.005 g DIR coupler D-1
0.08 g DIR coupler D-2
0.165 g CPM

13th layer (Mikrat layer)

0.16 g AgNO ₃

a Mikrat-Ag (Br, I) emulsion, average grain diameter 0.06 µm, 0.5 mol% iodide
1.1 g gelatin
0.35 g UV absorber UV-2
0.35 g CPM

14th layer (protective and hardening layer)

0.25 g gelatin
0.75 g of curing agent of the formula

so that the total layer structure after hardening has a swelling factor <3.5 would have.

Substances used in example 1:

Example 2

This example was the same as Example 1 except for the following changes:

2 layer

1.0 g AgNO ₃

a red-sensitive Ag (Br, I) emulsion with 4 mol% AgI, average grain diameter 0.55 µm
0.29 g C-1
0.012 g D-2
0.023 g RC-1
0.03 g YC-1
0.75 g gelatin
0.335 g CPM

3 layer

1.2 g AgNO ₃

a red-sensitive Ag (Br, I) emulsion with 4 mol% AgI, average grain diameter 0.84 µm
0.27 g C-1
0.006 g D-2
0.02 g RC-1
0.013 g YC-1
0.78 g gelatin
0.287 g CPM

4th layer

1.5 g AgNO ₃

a red-sensitive Ag (Br, I) emulsion with 10 mol% AgI, average grain diameter 1.23 µm
0.012 g D-1
0.02 g RC-1
0.02 g YC-1
1.10 g gelatin 0.1 g CPM

6th layer

0.55 g AgNO ₃

a green-sensitive Ag (Br, I) emulsion with 4 mol% AgI, average grain diameter 0.55 µm
0.31 g M-1
0.02 g YM-1
0.016 g D-2
0.95 g gelatin
0.026 g CPM

7th layer

1.3 g AgNO ₃

a green-sensitive Ag (Br, I) emulsion with 4 mol% AgI, average grain diameter 0.84 µm
0.24 g M-1
0.024 g YM-1
0.011 g YM-2
0.019 g D-2
0.64 g gelatin
0.044 g CPM

8th layer

1.55 g AgNO ₃

a green-sensitive Ag (Br, I) emulsion with 10 mol% AgI, average grain diameter 1.23 µm
0.06 g M-1
0.024 g YM-1
0.009 g YM-2
0.016 g D-1
0.75 g gelatin
0.045 g CPM

10th layer

0.50 g AgNO ₃

a blue-sensitive Ag (Br, I) emulsion with 7 mol% AgI, average grain diameter 0.65 µm
0.40 g Y-1
0.003 g D-2
1.2 g gelatin
0.403 g CPM

11th layer

0.67 g AgNO ₃

a blue-sensitive Ag (Br, I) emulsion with 7 mol% AgI, average grain diameter 0.8 µm
0.31 g Y-1
0.008 g D-2
0.65 g gelatin
0.316 g CPM

12th layer

1.25 g AgNO ₃

a blue sensitive Ag (Br, 1) emulsion with
11 mol% AgI, average grain diameter 1.33 µm
0.16 g Y-1
0.015 g D-1
0.85 g gelatin
0.171 g CPM

The densities after white exposure and after the 3 selective exposures in red, green and blue were determined for both materials. For this purpose, a gray wedge was exposed with white light (standard daylight) and the same was done with the interposition of a blue, green and red pull-out filter. The processing was carried out in a color negative process, which is described in "The British Journal of Photography", 1974, pages 597 and 598. In the following table, ΔD ^0.5 , ΔD ^1.0 , ΔD ^1.5 mean the difference in density between selective and white exposure. This density difference for exposure is 0.5, 1.0 and 1.5 log. Units specified above the respective reference exposure values of the white and spectral exposure. The reference exposure value is the exposure that produces a density of 0.2 over fog. The values obtained are shown in Table 1.

The results in the table show that the material 1 in the case of underexposure, unsatisfactory color saturation and, moreover, has a striking walk towards better color saturation when overexposed. The material 2 according to the invention shows good color saturation even when underexposed, which changes relatively little with increasing exposure.

Claims (5)

1. Color photographic silver halide material, for each of the three spectral ranges blue, green and red has at least two silver halide emulsion layers different in their photographic sensitivity, characterized in that the layers are matched to one another in such a way that

• a) the 0.5 logarithmic units greater selective exposure in one of the three spectral ranges than is necessary to achieve a density of 0.2 via fog, after processing a density which is at least 0.1 higher (density difference ΔD ^0.5 ) in the negative in the complementary color results than in the case of white exposure, which is also 0.5 logarithmic units larger than the white exposure, which produces a density of 0.2 via fog,
• b) the selective exposure greater by 1.0 logarithmic units in one of the three spectral ranges than is necessary to achieve a density of 0.2 via fog, after processing results in a density difference ΔD ^1.0 which is at most twice the density difference ΔD Is ^0.5 and
• c) the selective exposure greater by 1.5 logarithmic units in one of the three spectral ranges than is necessary to achieve a density of 0.2 via fog results in a density difference ΔD ^1.5 after processing which does not exceed the 2.5- times the density difference ΔD is ^0.5 .

2. Color photographic silver halide material according to claim 1, characterized ge indicates that the selective exposures (a), (b) and (c) in the same spectral color. 3. Color photographic silver halide material according to claim 1, characterized characterized in that selective exposures (a), (b) and (c) in all specs central areas.   4. Color photographic silver halide material according to claim 1, characterized ge indicates that the silver halide emulsion layer for at least one of the spectral ranges with the highest photographic sensitivity contains a DIR coupler that cleaves a diffusible inhibitor. 5. Color photographic silver halide material according to claim 1, characterized ge indicates that the silver halide emulsion layer has the highest photographic sensitivity contains a silver halide emulsion, the The proportion of AgI is at least 4 mol% greater than the proportion of AgI all emulsions in the silver halide emulsion layers of the same color sensitivity, but less photographic sensitivity.