DE19650082A1 - Colour photographic material sensitised with hydrazine derivative without excessive deterioration during storage - Google Patents

Abstract

In colour photographic silver halide (AgX) material, with a base and light-sensitive AgX emulsion layer(s) containing colour coupler(s), the AgX emulsion layer contains hydrazine derivative(s) of formula (I) and hydroxamic acid compound(s) of formula (II): (R1)(R2)N-N(R3)(R4) (I) R5-C(=O)-N(OH)-R6 (II) in which R1, R2, R3, R4 = an optionally substituted alkyl, aryl or hetaryl group; or R1 and R2 or R1 and R3 together and R2 and R4 together = a group completing a non-aromatic 5-8-membered heterocycle; and one of R1 to R4 has substituent(s) by which (I) is adsorbed on AgX; R5 = an optionally substituted alk(en)yl, aryl, alkylamino, arylamino, alkoxy, aryloxy or heterocyclic group; R6 = hydrogen (H) or an optionally substituted alkyl or aryl group.

Description

The invention relates to a color photographic silver halide material, in particular a color negative film, with high sensitivity and excellent latent image stability.

It is known the sensitivity of black and white photographic materials to increase by adding hydrazine derivatives. You transfer this teaching Color photographic materials, especially color negative films, are indeed obtained also an increase in sensitivity, but at the same time also an unimportant one desired increase in veil with long-term storage and an undesirable Change in the latent image.

The addition of known latent image stabilizers results in the combination with the Hydrazine derivatives do not achieve the desired result, but on the contrary further increase in the storage veil and to the undesirable change of Latent image.

The object of the invention was therefore to provide stabilizers which Combination with hydrazine derivatives whose ability to increase sensitivity increase, not diminish, prevent the increase in storage veil, and that Stabilize latent image.

It has now been found that this task is accomplished by adding certain Hydroxamic acid derivatives is dissolved.

The invention therefore relates to a color photographic silver halide material with a support and at least one light-sensitive silver halide emulsion layer which is assigned at least one color coupler, characterized in that the silver halide emulsion layer contains at least one compound of the formula I and at least one compound of the formula II:

wherein
R ₁ , R ₂ , R ₃ and R ₄ independently of one another unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl or R ₁ and R ₂ or R ₁ and R ₃ together and R ₂ and R ₄ together the rest Members of a non-aromatic 5- to 8-membered heterocycle, with the proviso that one of the radicals R ₁ to R ₄ is substituted by at least one substituent by which the compound of the formula I is adsorbed on a silver halide, and
R _{5 is} unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted aryl, unsubstituted or substituted alkylamino, unsubstituted or substituted arylamino, unsubstituted or substituted alkoxy, unsubstituted or substituted aryloxy or an unsubstituted or substituted heterocyclic group
R _{6 is} hydrogen, unsubstituted or substituted alkyl or unsubstituted or substituted aryl.

R ₁ and R ₂ together preferably represent the remaining members of a 5- to 7-membered saturated heterocycle,
R ₃ C ₁ -C ₄ alkyl, especially methyl and
R ₄ one through the rest

-LR ₇

substituted C ₁ to C ₄ alkyl radical, where
L a link and
R _{7 is} a radical of 4-hydroxy-1,3,3a, 7-tetraazainden, 3-mercapto-1,2,4-triazole or 5-mercaptotetrazole.

Suitable links L are -NHCO-CH ₂ -, -CONH-, -OCOCH ₂ -, -COO-, -NHCONH-phenylene-, the former atom being linked via the alkyl group to the hydrazine grouping.

R ₅ is preferably an unsubstituted or substituted C ₁ -C ₂₀ alkyl radical; R ₆ is preferably hydrogen or a C ₁ -C ₄ alkyl radical.

Suitable examples of formula I are

Further suitable hydrazine derivatives can be found in EP-A-0 652 470.

Suitable examples of formula II are:

Further suitable hydroxamic acid derivatives can be found in EP-A-0 698 814.

The compounds of formulas I and II are especially the highest sensitive layers of a material that is used for at least one Spectral range at least two layers of different sensitivity points. Preferably the compounds of formulas I and II are the highest red sensitive layer added.

In a preferred embodiment, the following amounts are used:
Compound of formula I: 10 ^-5 to 10 ^-3 mol / mol silver halide of the layer in question; preferably 3.10 ^-4 to 5.10 ^-3 mol / mol silver halide of the layer in question;
Compound of formula II: 10 ^-2 to 10 ^-2 mol / mol silver halide of the layer in question; preferably 3.10 ^-2 to 6.10 ^-2 mol / mol silver halide of the layer in question.

The compound of the formula I is preferred together with the spectral sensor lizer and the compound of formula II together with the color coupler give.

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 sil over color bleaching process.

The photographic materials consist of a support on which at least one photosensitive silver halide emulsion layer is applied. As a carrier thin films and foils are particularly suitable. An overview of carriers  materials and auxiliary layers applied to their front and back are in Research Disclosure 37254, Part 1 (1995), p. 285.

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 vary be arranged. This is shown for the most important products:

Color photographic films such as color negative films and color reversal films show in in the order given below on the support 2 or 3 rotsensit liche, cyan-green coupling silver halide emulsion layers, 2 or 3 green temp sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue sensitive, yellow-coupling silver halide emulsion layers. The layers same spectral sensitivity differ in their photographic emp sensitivity, with the less sensitive sub-layers usually closer arranged to the carrier than the higher sensitive sub-layers.

Between the green sensitive and blue sensitive layers is more common a yellow filter layer, which prevents blue light from entering the to get layers below.

The possibilities of the different layer arrangements and their out effects on the photographic properties are described in J. Int. Rec. Mats., 1994, Vol. 22, pages 183-193.

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 halo on the carrier genide emulsion layer, a green-sensitive, purple-coupling silver halide emulsion 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 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).

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.

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 and in Research Disclosure 37038, Part II (1995), p. 80. The maximum absorption of that from the couplers and the color developer oxidation Product-formed dyes are 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.

The usually between layers of different spectral sensitivity arranged non-light-sensitive intermediate layers can contain agents which an undesirable diffusion of developer oxidation products from a photosensitive to another photosensitive layer with different prevent spectral sensitization.

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, in 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.

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 layer support made from cellulose triacetate. 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 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of AgNO ₃ .

1st layer (antihalo layer)

0.3 g black colloidal silver
1.2 g gelatin
0.4 g UV absorber UV 1
0.02 g tricresyl phosphate (CPM)

2nd layer (intermediate layer)

0.25 g AgNO ₃

an AgBrI emulsion, average grain diameter 0.07 µm, 0.5 mol% AgI
1.0 g gelatin

3rd layer (low red sensitive layer)

2.7 g AgNO ₃

a spectrally red-sensitized Ag (Br, I) emulsion with 4 mol% iodide, average grain diameter 0.5 µm
2.0 g gelatin
0.88 g of colorless coupler C-1
0.02 g DIR coupler D-1
0.05 g colored RC-1 coupler
0.07 g colored coupler YC-1
0.75 g CPM

4th layer (highly red-sensitive layer)

2.2 g AgNO ₃

the spectrally red-sensitized Ag (Br, I) emulsion, 12 mol% iodide, average grain diameter 1.0 µm
1.8 g gelatin
0.19 g of colorless coupler C-2
0.17 g CPM

5th layer (intermediate layer)

0.4 g gelatin
0.15 g white coupler W-1
0.06 g Al salt of aurintricarboxylic acid

6th layer (low green sensitive layer)

1.9 g AgNO ₃

a spectrally green-sensitized Ag (Br, I) emulsion, 4 mol% iodide, average grain diameter 0.35 µm
1.8 g gelatin
0.54 g of colorless coupler M-1
0.24 g DIR coupler D-1
0.065 g colored coupler YM-1
0.6 g CPM

7th layer (highly green-sensitive layer)

1.25 g AgNO ₃

a spectrally green-sensitized Ag (Br, I) emulsion, 9 mol% iodide, average grain diameter 0.8 µm
1.1 g gelatin
0.195 g of colorless coupler M-2
0.05 g colored coupler YM-2
0.245 g CPM

8th layer (yellow filter layer)

0.09 g of yellow colloidal silver
0.25 g gelatin
0.08 g Scavenger SC1
0.40 g formaldehyde scavenger FF-1
0.08 g CPM

9th layer (low blue-sensitive layer)

0.9 g of a spectrally blue-sensitized Ag (Br, I) emulsion, 6 mol% iodide, average grain diameter 0.6 µm
2.2 g gelatin
1.1 g of colorless coupler Y-1
0.037 g DIR coupler D-1
1.14 g CPM

10th layer (highly blue-sensitive layer)

0.6 g AgNO ₃

a spectrally blue-sensitized Ag (Br, I) emulsion, 10 mol% iodide, average grain diameter 1.2 µm,
0.6 g gelatin
0.2 g colorless coupler Y-1
0.003 g DIR coupler D-1
0.22 g CPM

11th layer (Mikrat layer)

0.06 g AgNO ₃

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

12th layer (protective and hardening layer)

0.25 g gelatin
0.75 g of curing agent of the formula

so that the total layer structure had a swelling factor ≦ 3.5 after curing.
Substances used in example 1:

After exposing a gray wedge, the material is subjected to a color negative Processed in the "The British Journal of Photography" 1974, pages 597 and 598.  

In the case of the layer structures 1B-1E, the compounds shown in Table 1 were also added to the fourth layer in the amounts stated (mol / mol silver halide):
The following properties were checked:
E _0.2 : Relative sensitivity behind red filter 0.2 density units above minimum density
E _0.8 : Relative sensitivity behind red filter 0.8 density units above minimum density
E LB | 0.2 or E LB | 0.8 corresponding values after storing the exposed samples for 6 weeks at 25 ° C / 60% rel. Humidity.
D _min : Veil behind red filter in absolute density values E _0.2 and E _0.8 are set for structure 1A 100.

Compound 1-3 together with the sensitizer in alcoholic solution of the silver halide emulsion; II-5 of the coupler dispersion and ST-1 added as an alkaline solution to the casting solution for the 4th layer.
ST-1 is thiazolidine carboxylic acid.
1A to 1D are comparative experiments; 1E is in accordance with the invention.

Only experiment 1E with the combination according to the invention leads to an increase sensitivity with a stable latent image and without increasing the fog.

Claims (4)

1. Color photographic silver halide material with a support and at least one light-sensitive silver halide emulsion layer to which at least one color coupler is assigned, characterized in that the silver halide emulsion layer contains at least one compound of the formula I and at least one compound of the formula II.
wherein
R ₁ , R ₂ , R ₃ and R ₄ independently of one another unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl or R ₁ and R ₂ or R ₁ and R ₃ together and R ₂ and R ₄ together remaining members of a non-aromatic 5- to 8-membered heterocycle, with the proviso that one of the radicals R ₁ to R ₄ is substituted by at least one substituent by which the compound of the formula I is adsorbed on a silver halide, and
R _{5 is} unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted aryl, unsubstituted or substituted alkylamino, unsubstituted or substituted arylamino, unsubstituted or substituted alkoxy, unsubstituted or substituted aryloxy or an unsubstituted or substituted heterocyclic group
R _{6 is} hydrogen, unsubstituted or substituted alkyl or unsubstituted or substituted aryl. 2. A silver halide color photographic material as claimed in claim 1, wherein
R ₁ and R ₂ together are the remaining members of a 5- to 7-membered saturated heterocycle,
R ₃ C ₁ -C ₄ alkyl,
R _{4 is} a C ₁ -C ₄ alkyl radical substituted by the radical -LR ₇ ,
L a link,
R _{7 is} a residue of 4-hydroxy-1,3,3a, 7-tetraazainden, 3-mercapto-1,2,4-triazole or 5-mercaptotetrazole
R _{5 is} an unsubstituted or substituted C ₁ -C ₂₀ alkyl radical and
R _{6 is} hydrogen or a C ₁ -C ₄ alkyl radical. 3. Color photographic silver halide material according to claim 1, wherein the compound of formula I in an amount of 10 ^-5 to 10 ^-3 mol / mol of silver halide and the compound of formula II in an amount of 10 ^- 2 to 10 ^-1 mol / mol Silver halide can be used. 4. Color photographic silver halide material, characterized in that the compounds of formulas I and II of the ultra red sensitive layer be added and the material at least two red sensitive Has layers of different sensitivity.