DE19632927A1 - Colour photographic material with coupler solvent stabilising image dye, especially yellow dye - Google Patents

Abstract

In colour photographic material with red-, green- and blue-sensitive silver halide (AgX) emulsion layer(s) containing a cyan, magenta and yellow coupler respectively and optionally other light-insensitive layers, at least one emulsion or light-insensitive layer contains a cyclic imide, cyclic carbamate or cyclic urea with >= 8 carbon (C) atoms, with the exception of N-n-amylsuccinimide.

Description

The invention relates to a color photographic recording material with light sensitive silver halide emulsion layers and their associated color couplers in at least one photosensitive or non-photosensitive Layer a compound to improve the stability of the chromogenic Development contains image dyes produced.

The stability of chromogenic development of color coupler-containing color Photographic dyes produced image recording materials allows many times wish you left. On the one hand, this relates to the stability to the action of light (light fading) and on the other hand, the stability to the action damp or dry heat (dark fading).

In US-A-5 089 380 and in EP-A-0 591 861 the compound is N-n-amyl succin imid described as permanent coupler solvent.

It has been found that by using higher fatty cyclic Imides, carbamates or ureas the stability chromogenically developed image dyes, in particular the chromogenically developed yellow partial color image ver can be improved.

The invention is a color photographic recording material with at least one red-sensitive silver halide emulsion layer containing a cyan coupler, at least one green-sensitive silver halide emuls sion layer, which is associated with a magenta coupler, at least one blue sensitive silver halide emulsion layer associated with a yellow coupler is, and optionally other non-photosensitive layers, characterized ge indicates that at least one photosensitive or non-photosensitive Silver halide emulsion layer, a cyclic imide, a cyclic carbamate or contains a cyclic urea with not less than 8 carbon atoms in total, excluding the compound N-n-amyl succinimide. Preferably, the correspond mentioned compounds of one of the formulas I, II and III:

in which mean:
R¹¹, R²¹, R³¹ and R³² (optionally independently of one another): alkyl, cycloalkyl or aryl;
Q¹, Q² and Q³ are the radical necessary to complete a 5- to 8-membered non-aromatic ring;
wherein the total number of C atoms in the case of the compounds of the formula I is not less than 10, and in the case of the compounds of the formulas II and III not less than 9.

Preferably Q¹, Q² and Q³ are alkylene or cyclo alkylene. The 5- to 8-membered ones completed by Q¹, Q² and Q³ do not aromatic rings may be substituted or fused in turn contain saturated or unsaturated carbocyclic or heterocyclic rings, z. B. fused cyclohexane, cyclohexene or dioxole rings.

One represented by one of R¹¹, R²¹, R³¹ and R³², or therein or in Q¹, Q² or Q³ contained alkyl group may be straight-chain or branched and For example, contain up to 20 carbon atoms. It can also be substituted. A Aryl group is especially phenyl or substituted phenyl.

Examples of possible substituents on one completed by Q¹, Q² or Q³ substituted 5- to 8-membered non-aromatic ring or at one through R¹¹, R²¹, R³¹ or R³² shown alkyl or aryl group are: halogen, alkyl, aryl, Acyl, alkoxy, aryloxy, acyloxy and acylamino.

An acyl group contained in R¹¹, R²¹, R³¹, R³², Q¹, Q² or Q³ can be derived its from an aliphatic or aromatic carboxylic acid, an aliphatic  or aromatic carbamic acid, an aliphatic or aromatic carbon acid semi-ester, an aliphatic or aromatic sulfonic acid, an aliphati or aromatic sulfinic acid, an aliphatic or aromatic Amidosulfonic acid, an aliphatic or aromatic phosphorus or phosphone acid.

In a preferred embodiment of the invention Q¹, Q² or Q³ an aliphatic radical to complete a 5- or 6-membered ring and R¹¹, R²¹, R³¹ and R³² are alkyl.

In a further preferred embodiment of the invention, the compound one of the formulas I, II and III in one of the color coupler-containing layers. You will this advantageous together with the relevant color coupler in the Layer introduced and takes over all or part of the role of an oil bildners or coupler solvent.

Examples of suitable compounds of the formulas I, II and III are below specified.

The compounds of the invention are in the layers of farbfotografi generally in a concentration of 10-2,000 mg / m², preferably 20-1,000 mg / m² and more preferably from 30-600 mg / m², used. The incorporation is optionally carried out together with the relevant color coupler or other additives, using conventional Emulsification.

The use of the compounds according to the invention has an advantageous effect the stability of the image dyes generated in chromogenic development. When used with yellow couplers or cyan couplers, there is one Improvement of the stability of the yellow dye against the action of light and damp heat. When used together with magenta couplers in particular improves the light stability of the developed dye.

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 method or the Sil berfarbbleich method.

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

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

Depending on the type of photographic material, these layers may be different be arranged. This is illustrated for the main products:

Color photographic films such as color negative films and color reversal films exhibit the sequence indicated below on the carrier 2 or 3 rotempfind pale cyan silver halide emulsion layers, 2 or 3 greenemp 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 sublayers usually closer are 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 attached, the blue light prevents it, in the to reach underlying layers.

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

Color photographic paper, which is generally much less sensitive to light as a color photographic film, has the order given below usually a blue-sensitive, yellow-coupling silver halo on the support genisemulsion layer, a green sensitive, purplish coupling silver halide emulsion layer and a red-sensitive, cyan silver halide emulsion layer on; the yellow filter layer can be omitted.

Deviations from the number and arrangement of the photosensitive layers can to achieve certain results. For example, you can all highly sensitive layers to a layer package and all low-sensitivity layers to another layer package in a photographic film summarized to increase the sensitivity (DE 25 30 645).  

Essential constituents 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 on suitable silver halide emulsions, their preparation, ripening, Stabilization and spectral sensitization including appropriate spectral sensitizers can be found in Research Disclosure 37254, Part 3 (1995), p. 286 and in Research Disclosure 37038, Part XV (1995), p. 89.

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

For color couplers see Research Disclosure 37254, part 4 (1995), p. 288 and Research Disclosure 37038, Part II (1995), p. 80. The maximum absorption from the couplers and the color developer oxidation product formed dyes is preferably in the following areas: Yellow coupler 430 to 460 nm, magenta coupler 540 to 560 nm, cyan coupler 630 to 700 nm.

Color couplers used according to the invention for producing the yellow Teilfarbenbil of (yellow coupler) correspond to the following formula IV

in which mean:
R¹ is alkyl, cycloalkyl, aryl or an optionally cyclic amino group;
R² is H or a radical cleavable under the conditions of chromogenic development;
R³ is halogen or alkoxy;
R⁴H or a radical such as R³;
R⁵ is H, alkoxy, acylamino, alkoxycarbonyl, carbamoyl or sulfamoyl.

The acyl radical in an acylamino group represented by R⁵ is the same Way defined as for the formulas I, II and III.

Suitable examples are:

Color couplers for generating the purple partial color image (Magentakuppler) are in the regulator couplers of the type of 5-pyrazolone of indazolone or pyra zoloazole. The pyrazoloazoles preferably used according to the invention correspond the formula V

in which mean:
Y¹ is a radical cleavable under the conditions of chromogenic development;
R⁶ alkyl;
L _a and L _b (independently of each other), an N atom or a methine group of the formula

wherein R ^{s is} alkyl or aryl optionally with further substituents. Preferably, one of L _a and L _{b is} an N atom, the other is a methine group.

Suitable examples are:

Color coupler for producing the cyan partial color image (cyan coupler) preferably correspond to the formula VI

in which mean:
Y 2 H or a radical which can be eliminated under the conditions of chromogenic development;
R⁷ is alkyl, acylamino or carbamoyl;
R⁸ is alkyl, acylamino or together with R⁹ is a radical to complete a fused carbocyclic or heterocyclic, 5- or 6-membered, optionally aromatic ring;
R⁹ is alkyl, acylamino or together with R⁸ a radical to complete a fused carbocyclic or heterocyclic, 5- or 6-membered, optionally aromatic ring.

The acyl radical in an amino group represented by R⁸ or R⁹ is the same Way defined as for the formulas I, II and III.

Suitable examples of cyan couplers are:

In color photographic films are used to improve sensitivity, grainy Speed, sharpness and color separation are often used in the reaction with the developer oxidation product release compounds that are photographically are effective, for. B. DIR couplers which cleave a development inhibitor.

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

The most hydrophobic color couplers, but also other hydrophobic components of Layers are usually dissolved in high boiling organic solvents or dispersed. These solutions or dispersions are then dissolved in an aqueous Binder solution (usually gelatin solution) and emulsified after the  Dry the layers as fine droplets (0.05 to 0.8 microns in diameter) in the Layers in front.

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

The usually between layers of different spectral sensitivity angeges arranged non-photosensitive intermediate layers may contain agents that an undesirable diffusion of developer oxidation products from a light sensitive in another photosensitive layer with different spek prevent trol sensitization.

Suitable compounds (white couplers, scavengers or EOP scavengers) can be found in Research Disclosure 37254, Part 7 (1995), p. 292 and Research Disclosure 37038, Part III (1995), p. 84.

The photographic material may also contain UV light absorbing compounds, white toners, spacers, filter dyes, formalin scavengers, light stabilizers, anti-oxidants, D _min dyes, additives for improving the dye, coupler and white stability and for reducing the color fog, plasticizers (lattices) , Biocide and other included.

Suitable compounds are found in Research Disclosure 37254, Part 8 (1995), p. 292 and Research Disclosure 37038, Parts IV, V, VI, VII, X, XI and XIII (1995), P. 84 ff.

The layers of color photographic materials are usually cured, i. h., that used binders, preferably gelatin, by suitable chemical Networked process.

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

After imagewise exposure, color photographic materials become their character processed according to different methods. Details of the Ver  Driven and required chemicals are described in Research Disclosure 37254, Part 10 (1995), p. 294 and Research Disclosure 37038, parts XVI to XXIII (1995), p. 95 et seq., Together with exemplary materials.

example 1

A color photographic recording suitable for a fast-processing process material was prepared by applying to a support made of both sides Polyethylene coated paper, the following layers in the specified Rei were applied. The quantities refer in each case to 1 m². For the Silberhalogenidauftrag the appropriate amounts of AgNO₃ are give.

Sample 1

Layer 1 (substrate layer):

0.20 g of gelatin

Layer 2 (blue-sensitive layer):
blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 microns), from 0.50 g AgNO₃, with

1.38 g of gelatin
0.60 g yellow coupler XY-1
0.60 g of tricresyl phosphate (TKP)
0.15 g of dye stabilizer XST-1

Layer 3 (protective layer):

1.10 g of gelatin
0.04 g of 2,5-di-tert-octylhydroquinone
0.04 g oil former XOF-1
0.04 g of compound XSC-1

Layer 4 (green-sensitive layer):
green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, mean grain diameter 0.45 μm) of 0.25 g AgNO₃, with

1.08 g of gelatin
0.25 g magenta coupler XM-1
0.20 g of dye stabilizer XST-2
0.10 g of dye stabilizer XST-3
0.31 g dibutyl adipate (DBA)

Layer 5 (UV protection layer):

1.15 g of gelatin
0.40 g UV absorber XUV-1
0.20 g UV absorber XUV-2
0.025 g of 2,5-dioctylhydroquinone
0.02 g of compound XSC-1
0.20 g of oil former XOF-2
0.04 g TKP

Layer 6 (red-sensitive layer):
red sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 microns) from 0.30 g AgNO₃, with

0.75 g of gelatin
0.36 g of cyan coupler XC-1
0.36 g TKP

Layer 7 (UV protection layer)

0.35 g of gelatin
0.15 g UV absorber XUV-1
0.05 g UV absorber XUV-2
0.15 g of oil former XOF-2

Layer 8 (protective layer):

0.90 g of gelatin
0.30 g of hardener XH-1.

In sample 1 the following compounds were used:

Samples 2-19

Samples 2-19 were prepared as sample 1 with the difference that in the Layer 2 TKP equal in quantity by the specified in Table 1 oil former was exchanged.

As comparative compounds were used:

The samples were then placed behind a graduated grayscale wedge Exposed U449 filter and processed as follows:

a) Color developer - 45 s - 35 ° C Triethanolamine | 9.0 g N, N-diethyl 4.0 g diethylene glycol 0.05 g 3-methyl-4-amino-N-ethyl-N-methane-sulfonamidoethyl-aniline sulfate 5.0 g potassium 0.2 g triethylene 0.05 g potassium carbonate 22 g potassium hydroxide 0.4 g Ethylenediaminetetraacetic acid disodium salt 2.2 g potassium chloride 2.5 g   1,2-dihydroxybenzene-3,4,6-trisulfonic acid trisodium salt 0.3 g Make up to 1000 ml with water; pH 10.0

b) Bleach-fix bath - 45 s - 35 ° C Ammonium thiosulphate | 75 g sodium bisulfite 13.5 g ammonium acetate 2.0 g Ethylenediaminetetraacetic acid (ferric ammonium salt) 57 g Ammonia 25% 9.5 g Top up with vinegar to 1 000 ml; pH 5.5

c) watering - 2 min - 33 ° C

Subsequently, the maximum yellow density (D _max (gb)) was measured (Table 1). In addition, all samples were irradiated with the light of a xenon lamp normalized for daylight at 20x10⁶ lux * h, after which the percentage gb density decrease at initial density D _gb = 1.0 (Table 1, ΔD _1.0 ) was determined. Furthermore, exposed and processed samples for 42 days at 85 ° C and 50% rel. Stored dark and then determined the percentage decrease of the gb-maximum density (Table 1, ΔD _max ).

Table 1 (V: comparison, E: according to the invention)

As can be seen from Table 1, the compounds of the invention improve the Dye stability noticeably, but without color as the comparison compounds prey.  

Example 2 Samples 20-29

The samples 20-29 are prepared as sample 1 with the difference that in the Layer 4 dibutyl adipate equal in quantity against the oil former indicated in Table 2 was exchanged.

The samples were then exposed under a graduated gray wedge through a U531 filter and processed as described in Example 1. Then, the magenta maximum density (D _max (pp)) was measured (Table 2). Furthermore, the samples were irradiated with the light of a normalized xenon lamp at 15-10⁶ lux h. Thereafter, the percent density decrease was determined at initial densities D = 0.6 (ΔD _0.6 ) and D = 1.4 (ΔD _1.4 ) (Table 2).

Table 2 (V: comparison, E: according to the invention)

As Table 2 shows, the compounds of the invention improve the light stabilizer The color yield was significantly higher than the comparison compounds V-2 and V-3 reduce.

Example 3 Samples 30-37

Samples 30-37 were prepared as sample 1 except that in the Layer 3 of the oil former XOF-1 equal in quantity through I-4, in layer 5 of the oil Former XOF-2 and TKP the same amount by II-2, in the layer 7 of the oil former XOF-2 equal in quantity by I-8 and finally in the layer 6 TKP same volume was replaced by the compounds shown in Table 3. It was also in samples 34-37, the cyan coupler XC-1 was exchanged by moles for XC-2.

XC2 6: 4 mixture of

The samples were then exposed behind a graduated gray wedge through an L662 filter and processed as described in Example 1. Then, the cyan maximum density (D _max (bg)) was measured (Table 3). Subsequently, the samples were irradiated with the light of a daylight xenon lamp of 30 × 10 -5 lux, after which the percentage density decrease was determined at an initial density of D _bg = 1.0 (ΔD _1.0 , Table 3). In addition, the samples were kept for 40 days at 85 ° C, 50% r. F. stored dark and the decrease in the maximum density determined (ΔD _max , Table 3).

Table 3 (V: comparison, E: according to the invention)

Table 3 shows that the compounds of the invention the Vergleichsverbindun are clearly superior.

Claims (7)

1. A color photographic recording material as claimed in at least one rotempfindli chen silver halide emulsion layer is a cyan coupler associated with at least one green-sensitive silver halide emulsion layer associated with a magenta coupler, halogenidemulsionsschicht at least one blue-sensitive silver that is associated with a yellow coupler, and, where appropriate further non-photosensitive layers, characterized in that at least one photosensitive silver halide emulsion layer or a non-photosensitive layer contains a cyclic imide, a cyclic carbamate or a cyclic urea having not less than 8 carbon atoms in total except for the compound Nn-amyl succinimide. 2. Recording material according to claim 1, characterized in that the cyclic imide of the formula I corresponds to the cyclic carbamate of the formula II and the cyclic urea of the formula III in which mean:
R¹¹, R²¹, R³¹ and R³² (optionally independently of one another): alkyl, cycloalkyl or aryl;
Q¹, Q² and Q³ are the radical necessary to complete a 5- to 8-membered non-aromatic ring;
wherein the total number of C atoms in the case of the compounds of the formula I is not less than 10, and in the case of the compounds of the formulas II and III not less than 9. 3. Recording material according to claim 2, characterized in that Q¹, Q² and Q³ is an aliphatic radical to complete a 5- or 6- membered ring and R¹¹, R²¹, R³¹ and R³² are alkyl or cyclo alkyl. 4. Recording material according to one of claims 1-3, characterized gekenn characterized in that the cyclic imide, the cyclic carbamate or the cyclic Urea is contained in a color coupler-containing layer. 5. A recording material according to claim 4, characterized in that the cyclic imide, the cyclic carbamate or the cyclic urea is used in combination with a yellow coupler of the following formula in which mean:
R¹ is alkyl, cycloalkyl, aryl or an optionally cyclic amino group;
R² is H or a radical cleavable under the conditions of chromogenic development;
R³ is halogen or alkoxy;
R⁴H or a radical such as R³;
R⁵ is H, alkoxy, acylamino, alkoxycarbonyl, carbamoyl or sulfamoyl. 6. A recording material according to claim 4, characterized in that the cyclic imide, the cyclic carbamate or the cyclic urea in combination with a comonomer coupler of the following formula V is used in which mean:
Y¹ is a radical cleavable under the conditions of chromogenic development;
R⁶ alkyl;
L _a and L _b (independently of each other), an N atom or a methine group of the formula wherein R ^{s is} alkyl or aryl optionally with further substituents. 7. A recording material according to claim 4, characterized in that the cyclic imide, the cyclic carbamate or the cyclic urea is used in combination with a cyan coupler of the following formula in which mean:
Y 2 H or a residue cleavable under the conditions of chromogenic development;
R⁷ is alkyl, acylamino or carbamoyl;
R⁸ is alkyl, acylamino or together with R⁹ is a radical to complete a fused carbocyclic or heterocyclic, 5- or 6-membered, optionally aromatic ring;
R⁹ is alkyl, acylamino or together with R⁸ a radical to complete a fused carbocyclic or heterocyclic, 5- or 6-membered, optionally aromatic ring.