DE4241532A1 - New N-alkyl- and alkoxy-amino-phenyl cyclic imine colour developer cpds. - with pyrrolidine, piperidine or hexa:methylene:imine ring, giving stable, light-fast image dyestuff cpds., suitable for high speed development - Google Patents

Abstract

The prodn. of a colour photograph comprises developing exposed colour photographic material contg. Ag halide (AgX) emulsion coat(s) in the presence of a colour coupler and a colour developer, which is a substd. N-(3-alkyl- or -alkoxy-4-aminophenyl)- pyrrolidine, -piperidine or -hexamethylenimine cpd. of formula (I) or its salt. Cpds. of formula (I) are new. R1 is alkyl or alkoxy; R2-R7 are each OH, COOH, SO3H, alkyl(thio), aryl(oxy), acyl(oxy), alkoxy, sulphinyl, sulphonyl, sulphamoyl, acylamino or sulphonamido or some but not all are H; m and n is 0 or 1. The photographic material pref. has blue-, green- and red- sensitive AgX emulsion(s) contg. yellow, magenta and cyan couplers respectively, in the given sequence, opt. with spacer coats, on a light-reflecting or transparent base. AgX consists of at least 98 mole-% AgCl and the colour developer time is less than 35 secs.. ADVANTAGE - Development is rapid and stable, esp. light-fast photographs are obtd..

Description

The invention relates to a process for the preparation color photographic images as well as new color developers links.

It is known to color photographic images by chromo development, d. H. in that one imagewise exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color Developer - developed, in accordance with the silver image resulting oxidation product of Ent Wicklersubstanzen with the color coupler to form a dye image reacts. As a color developer usually become aromatic, primary amino groups containing compounds containing, in particular those of the p-phenylenediamine type, whose one amino group two optionally substituted alkyl radicals substitui is tuiert.  

It is also known that by chromogenic development ment generated image dyes in different Extent under the influence of environmental conditions certain Undergo changes. This is particularly noticeable as far as the action of light is concerned.

Furthermore, it is known that the color developer for a on the rate of chromogenic evolution On the other hand also on the stability the image dyes produced.

There have been several attempts to color developers find it in the case of photographic supervision allow the currently common development time to fall below without a reduction of Stability of the image dyes in purchase or in Case of photographic transparencies Shortening or maintaining the development time stabi provide image dye. The well-known color developers But they are not enough in every way requirements.

The invention is based on the object, color developer for photographic recording materials, which allow rapid development and equal early stable, especially light stable image dyes deliver.

The invention relates to a process for the preparation a color photographic image by developing a exposed color photographic recording material,  the at least one silver halide emulsion layer contains, in the presence of a color coupler and a Color developer compound, characterized in that as the color developing agent, a compound of the formula I or their salt is used

in which mean
R ^{1 is} alkyl or alkoxy; R ² , R ³ , R ⁴ , R ⁵ H, -OH, -COOH, -SO ₃ H, alkyl, aryl, acyl,
R ⁶ , R ⁷ alkoxy, aryloxy, acyloxy, alkylthio, sulfinyl, sulfonyl, sulfamoyl, acylamino, sulfonamido,
wherein at least one of R ² to R ^{7 is} other than H;
m, n is 0 or 1.

An alkyl or alkoxy group represented by R ¹ preferably contains 1 to 4 carbon atoms and may be optionally substituted, e.g. By -OH, -OCH ₃ , -SO ₃ H, -COOH, -NHSO ₂ -CH ₃ .

An acyl group represented by R ² to R ⁷ (acyloxy, acylamino) may be derived from an aliphatic or aromatic carboxylic acid, an optionally N-atom substituted carbamic acid (e.g., carbamoyl or a carbonic acid monoester (e.g. B. alkoxycarbonyl).

A radical represented by R ² to R ⁷ may in turn be further substituted at C and / or N atoms. In particular, a represented by R ² to R ⁷ or contained therein alkyl, alkoxy or aryl group before geous with a polar, the solubility in aqueous medium promoting group substituted z. With -OH, -COOH, -NH-SO ₂ -CH ₃ .

The radicals R ² to R ⁷ may be arranged so configurationally on the hetero cyclic ring that the color development lerverbindungen be present in diastereomerically pure or enantio merenreiner form or as a mixture of stereoisomers.

Examples of color developers according to the invention are according to listed below.

The preparation of the compounds according to the invention can for example, according to the following synthesis scheme:

X = -NH ₂ substitutable group such as. B. Br, O-SO ₂ CH ₃ ;

V _i = R ⁱ or radical which can be converted into R ⁱ after completion of the ring closure;
i = 2, 3, 4, 5, 6, 7; n, m = 0, 1.

The introduction of the NH ₂ group at the precursor (V-) can be carried out in a simple manner according to the methods described in J. Am. Chem. Soc. 73, 3100 (1951). The color developers are isolated as salts of sulfuric acid, hydrochloric acid, hydrobromic acid, p-toluenesulfonic acid or 1,5-naphthalenedisulfonic acid.

Preparation of compound F-1

64.3 g of m-toluidine, 46.3 g of 1,4-dibromo-2-butanol and 2.3 g KI are refluxed in 200 ml of anhydrous ethanol for 24 h heated river. Ethanol is distilled off, distributing the Residue between 1000 ml of ethyl acetate and 200 ml of water. The organic phase is washed with water and over Dried magnesium sulfate. The solvent is absorbed completely distilled off under reduced pressure. The residue is recrystallized from petroleum ether / ethyl acetate. This gives 23.0 g of precursor V-1 in the form of a bright yellow solid of melting point mp = 69 ° C. V-1 will converted as described above into F-1 and 60% Yield as a colorless semisulfate, which at 239 ° C below Decomposition melts, isolated.

Production of F-15

229.9 g of (R, R) -1,4-O-dimethylsulfonylthreitol and 292.1 g m-Toluidine are heated to 170 ° C for 6 h. The reaction Mixture is then repeated several times with 500 ml each Ethyl acetate heated to boiling and filtered. The ver The combined organic phases are completely concentrated and the oily residue several hours with petrol ether / ethyl acetate (10: 1) stirred vigorously. filtration of the dye thus obtained and drying gives 147 g V-15, which without further purification as described in F-15 is transferred. F-15 is isolated as a semisulfate, which melts at 254 ° C with decomposition.  

In a preferred embodiment, the Farbent winding carried out in an aqueous developer, which ent ent a color developer compound according to the invention holds. For example, color development can be the negative color development or the color development to act in the context of a reversal process. The invention in accordance with color developer compounds in shape be transported by concentrates.

In the development, the usual conditions of Color development are observed. Usually finds development at a pH above 8, preferably way over 9.5 instead. The concentration of the colorant Winder connections depend on the circumstances, a concentration of about 4 to 40 mmol / l of ge ready-to-use developer solution is particularly preferred. In addition to the color developer verver Compounds may contain other color developing agents be used. Reference is made to Research Disclosure 17 643 of December 1978, section XX. The development can in the presence of pH buffers, development inhibitor ren, antifoggants, complexing agents to the water Hardening, preservatives, Entwicklungsbeschleu niger, competing couplers, concealment agents, Auxiliary developer compounds and viscosity modifier be referred to o.a. Research Disclosure, Section XXI.

The color developer compounds of the invention can but also in one or more layers of the verar processing color photographic recording material in  be contained inactive form and in processing under suitable conditions, e.g. B. by the action of Heat or by treatment with an alkaline asset Torbad be activated for color development.

The developer compound can, for example, in Form of their hydrochloric acid salts, sulfuric acid salts, phosphoric acid salts, phosphonic acid salts, p- Toluenesulfonic acid salts, benzodisulfonic acid salts, etc. be used. Furthermore, it is possible that the Color developer compound to an ion exchanger is present bound (DE-A-31 45 288).

The color developing agents may also be in the form of Precursor compounds are used which make up in development under alkaline conditions the Developer compound forms. Precursor compounds can For example, as Schiff bases, referenced is in this connection EP-A-0 074 763, page 16ff, or else capped as urethane or as ureido compounds (US Pat. No. 4,426,441).

Examples of color photographic materials associated with the color developers according to the invention are developed can, color negative films, color reversal films, farbfoto graphic paper or color reversal photographic paper.

Color photographic materials usually include at least three silver halide emulsion layers below different spectral sensitivity, at least  one red-sensitive, one green-sensitive and one red blue-sensitive silver halide emulsion layer, as well optionally intermediate layers and protective layers.

Essential components of the photographic emulsion layers are binders, photosensitive silver halide and color coupler.

The binder used is preferably gelatin. However, this can be syn or in part by other syn thetic, semisynthetic or naturally precom mende polymers are replaced. Synthetic gelatin substances are, for example, polyvinyl alcohol, poly- N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are included For example, other proteins such as albumin or casein, Cellulose, sugar, starch or alginates. semi-synthetic Gelatine substitutes are usually modified Natural products. Cellulose derivatives such as hydroxyalkylcellu loose, carboxymethylcellulose and phthalylcellulose as well Gelatin derivatives obtained by reaction with alkylation or acylating agents or by grafting on polymerizable monomers have been obtained Examples of this.

The binders should be over a sufficient amount functional groups, so that by implementation sufficiently resistant with suitable curing agents Layers can be generated. Such functional Groups are in particular amino groups, but also Carbo xyl groups, hydroxyl groups and active methylene groups.  

As the photosensitive component in the photogra fishing material silver halide can as Halide chloride, bromide or iodide or mixtures included. For example, the halide content at least one layer to 0 to 15 mol% of iodide, too 0 to 100 mol% of chloride and 0 to 100 mol% of Bromide exist. In the case of color negative and color Reversal films are typically silver bromide iodide in the case of color negative and color reversal paper or a corresponding material with transparent Layer support (display material) usually silver Chloride bromide emulsions with high chloride content up to pure silver chloride emulsions used. In a In such case, the silver halide is preferable at least 98 mol%, more preferably at least 99.5 mol%, of silver chloride. It can be about gend compact crystals that z. Eg regular cubic or octahedral or have transitional forms can. Preferably, however, can also be platelet-shaped Crystals are present whose average ratio from diameter to thickness is preferably at least 5: 1, wherein the diameter of a grain is defined as the Diameter of a circle with a circle content ent speaking the projected area of the grain. The Schich but can also be tabular silver halide have crystals in which the ratio of By diameter to thickness is much larger than 5: 1, z. Eg 12: 1 to 30: 1.  

The silver halide grains may also have a multiple ge have layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), wherein the halide composition and / or other modifications, such. B. doping of a individual grain areas are different. The middle Grain size of the emulsions is preferably between 0.2 μm and 2.0 μm, the particle size distribution can be both homo- as well as heterodisperse. Homodisperse grain Size distribution means that 95% of the grains no longer differ by ± 30% from the mean grain size. The Emulsions can also organi in addition to the silver halide contain silver salts, z. B. silver benzotriazolate or silver behenate.

There can be two or more types of silver halide emulsions, which are prepared separately, as a mixture be used.

The emulsions can be chemically mixed in the usual way and / or spectrally sensitized; You can also be stabilized by suitable additives. suitable chemical sensitizers, spectral sensitization Dyes and stabilizers are for example in Research Disclosure 17643 (December, 1978); Reference is made in particular to Chapters III, IV and VI.

Particularly suitable for spectral sensitization Dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.  

In particular, the following dyes - are ordered according to spectral regions - suitable:

1. as red sensitizers

9-ethylcarbocyanines with benzothiazole, benzselenazole or naphthothiazole as basic end groups, the in the 5- and / or 6-position by halogen, methyl, Methoxy, carbalkoxy, aryl can be substituted and 9-ethyl-naphthoxathia- or -selencarbo cyanine and 9-ethyl-naphthothiaoxa- and -benz imidazocarbocyanines, provided that the color at least one sulfoalkyl group on the hetero carry cyclic nitrogen.

2. as green sensitizers

9-Ethylcarbocyanine with benzoxazole, naphthoxazole or a benzoxazole and a benzothiazole as basic end groups and benzimidazocarbocyanines, which may also be further substituted and likewise at least one sulfoalkyl group on the hete must contain rocyclic nitrogen.

3. as blue sensitizers

symmetric or asymmetric benzimidazo, oxa, Thia- or selenocyanines with at least one Sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on aromati core, as well as Apomerocyanine with a Rhoda ningruppe.  

Sensitisers can be omitted if for a specific spectral range the Eigenempfindlich keits of the silver halide is sufficient, for example show the blue sensitivity of silver bromides.

The color photographic recording materials enthal usually in spatial and spectral allocation differed from the silver halide emulsion layers spectral sensitivity color coupler for generation different part color images cyan, magenta and Yellow.

Under spatial assignment is to be understood that the color coupler is in such a spatial relationship is located to the silver halide emulsion layer, that an interaction between them is possible, the a picture-like correspondence between the at the Development formed silver image and the color coupler generated color image permits. This is in the Rule achieved in that the color coupler in the Silver halide emulsion layer itself is included or in an adjacent thereto may not photosensitive binder layer.

By spectral allocation is meant that the Spectral sensitivity of each of the photosensitive Silver halide emulsion layers and the color of the each generated spatially associated color coupler Part color image in a certain relationship zuein different, each of the spectral sensitivities  (Red, green, blue) another color of the subject Partial color image (in general, for example, the colors cyan, Magenta or yellow in this order) is.

Each of the different spectrally sensitized Sil berhalogenemulsion layers may or may also be associated with multiple color couplers. If several Silver halide emulsion layers of the same spectral Sensitivity may exist, any of them contain a color coupler, these color couplers not necessarily identical. you should only at least during color development give almost the same color, usually one Color that is complementary to the color of the light, for the silver halide emulsion concerned layers are predominantly sensitive.

Color couplers for generating the partial color image cyan are usually phenol or α-naphthol type couplers; ge suitable examples are:

Color coupler for producing the purple partial color image are usually couplers of the type of 5-pyrazolone, the Indazolone or pyrazoloazole; suitable examples are for this

Pyrazoloazole couplers of the general formulas X and XI

are described, for example, in US-A-3,725,067 and US-A-4,540,654. In the formulas VIII and IX mean:
XH or a group releasable under the conditions of color development;
R ¹ , R ² , H, alkyl, aralkyl, aryl, alkoxy, Aroxy, alkyl thio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl, sulfamoyl, where these radicals may be further substituted.

Color couplers for generating the partial color image are yellow usually couplers with an open-chain keto methylene moiety, especially couplers of the type α-acylacetamide; suitable examples of this are α- Benzoylacetanilide couplers and α-pivaloylacetanilide couplers the formulas  

The color couplers can be 4-equivalent couplers but also about 2-equivalent couplers. Latter derive from the 4-equivalent couplers in that they contain a substituent in the coupling site th, which is split off during the clutch. To the 2 Equivalent couplers are those that are colorless are, as well as those that have an intense intrinsic color have, which disappears in the color coupling or replaced by the color of the generated image dye is (mask coupler), and the white couplers, which at Reak tion with color developer oxidation products in wesentli chen colorless products. To the 2-equivalent dome Furthermore, such couplers are to be reckoned in the Clutch point contain a cleavable residue, the upon reaction with color developer oxidation products in Freedom is set and thereby either directly or after the primary split-off remainder one or several further groups have been split off (eg DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic Effectiveness unfolded, z. B. as a development inhibitor or -accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR- or FAR couplers.  

The couplers used, d. H. especially the cyan group For example, formulas II, III, IV and V, which Magenta coupler, z. 2-equivalent or 4-equivalent Magenta couplers of the pyrazolone or pyrazole type loazoles, for example of the formulas VIII and IX, can also in polymeric form, for. B. as a polymer latex to Application reach.

High molecular color couplers are beschrie example in DE-C-1 2 97 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211. The high molecular color couplers are usually by polymerization of ethylenically unsaturated mono meren color couplers produced.

The usually between layers of different Spectral sensitivity is not arranged light sensitive interlayers may contain agents the unwanted diffusion of developer Oxidation products from a photosensitive to a other photosensitive layer with different prevent spectral sensitization.

Suitable agents that include scavengers or EOP scavengers are referred to in Research Disclosure 17 643 (Dec., 1978), Chapter VII, 17,842 (Feb. 1979) and 18,716 (Nov. 1979), page 650 and in EP-A-0 069 070, 0 098 072, 0 124 877, 0 125 522 described.

Examples of particularly suitable compounds are:  

The photographic material can also UV light ab sorbierende compounds, whiteners, spacers, filter dyes, light stabilizers, antioxidants, D _Min dyes, additives for improving the dye coupler and whitener stabilization and for reducing tion of the color fog, plasticizers (latices), biocides and other things included.

Color negative photographic materials are commonly used by developing, bleaching, fixing and watering or by developing, bleaching, fixing and stabilizing processed without subsequent watering, bleaching and fixing together to a processing step can be grasped. Leave as color developer compound to use all the developer compounds that the Possess ability in the form of their oxidation product with color couplers to Azomethin- or Indophenolfarbstof to react. Suitable color developer compounds are aromatic, at least one primary amino group containing p-phenylenediamine-type compounds, e.g. B. the following

Other useful color developers are, for example in J. Amer. Chem. Soc. 73, 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.

After the color development can be an acid stop bath or follow a watering.

Usually, the material is immediately after the Color development bleached and fixed. As a bleach can z. As Fe (III) salts and Fe (III) complex salts such Ferricyanides, dichromates, water-soluble cobalt complexes used. Particularly preferred are iron (III) Complexes of aminopolycarboxylic acids, in particular z. B.  of ethylenediaminetetraacetic acid, propylenediaminetetra acetic acid, diethylenetriaminepentaacetic acid, nitrilo triacetic acid, iminodiacetic acid, N-hydroxyethyl-ethyl lendiamintriacetic acid, alkyliminodicarboxylic acids and of corresponding phosphonic acids. Suitable as a bleach are still persulfates and peroxides, z. B. Hydrogen peroxide.

The bleach-fix or fixer is usually followed by one Irrigation, which is designed as countercurrent irrigation or from several tanks with their own water supply be stands.

Cheap results can be obtained by using one following final bath, the little or no Formaldehyde.

The watering can be full but by a stabilizer constantly replaced, usually in countercurrent to be led. This stabilizer takes on form aldehyde addition also the function of a final bath.

In color reversal materials is initially a development with a black and white developer whose oxida tion product not to react with the color couplers be is capable. It closes a diffuse Zweitbe clearing and then developing with a color developer, Bleaching and fixing.

Example 1

A color photographic recording material suitable for a rapid processing process was prepared by applying the following layers in the order given to a backing of polyethylene coated paper on both sides. The quantities are in each case based on 1 m ² . For the silver halide application, the appropriate amounts of AgNO ₃ are given.

Layer Structure 1

Layer 1 (substrate layer):
0.2 g of gelatin

Layer 2 (blue-sensitive layer):
blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average particle diameter 0.8 μm) from 0.63 g AgNO ₃ with
1.38 g of gelatin
0.95 g yellow coupler Y-9
0.40 g of dye stabilizer St-1
0.2 g white coupler W-1
0.29 g tricresyl phosphate (TKP)

Layer 3 (protective layer):
1.1 g of gelatin
0.06 g of 2,5-dioctylhydroquinone
0.06 g dibutyl phthalate (DBP)

Layer 4 (green-sensitive layer):
green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average particle diameter 0.6 μm) from 0.45 g AgNO ₃ with
1.08 g of gelatin
0.61 g magenta coupler M-3
0.21 g of dye stabilizer St-2
0.21 g of dye stabilizer St-3
0.08 g of 2,5-dioctylhydroquinone
0.34 g DBP
0.04 g TKP

Layer 5 (UV protection layer):
1.15 g of gelatin
0.6 g UV absorber UV-1
0.045 g of 2,5-dioctylhydroquinone
0.04 g TKP

Layer 6 (red-sensitive layer):
red sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, mean grain diameter 0.5 μm) from 0.3 g AgNO ₃ with
0.75 g of gelatin
0.36 g of cyan coupler C-24
0.36 g TKP

Layer 7 (UV protection layer):
0.35 g of gelatin
0.15 g UV absorber UV-1
0.2 g TKP

Layer 8 (protective layer):
0.9 g of gelatin
0.3 g of HM-1 curing agent
carbamoylpyridinium
CAS Reg. 65411-60-1.

In layer 2, the following compounds were used:

In layer 4 the following compounds were used.

In layer 5 and 7 the following compound (UV- Absorber UV-1) used.

Layer structure 2

Layer 2 was layered in the same way Construction 1 manufactured with the difference that in the Layer 4 of the magenta coupler M-3 and the Farbstoffsta bilisers St-2 and St-3 were replaced by XM-1 (0.41 g) and St-4 (0.32 g) and St-5 (0.10 g).  

Trial 1 comparison

Samples of the layer structures 1 and 2 were behind a graduated gray wedge exposed and with the following listed processing baths in the specified Processed (Method A and Method B).

method A

• a) Color developer bath - 45 s - 35 ° C Triethanolamine | 9.0 g NN-diethyl 4.0 g diethylene glycol 0.05 g 3-Methyl-4-amino-N-ethyl-N-methanesulfonamidoethyl aniline sulfate (P-2) 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 fill with vinegar to 1000 ml; pH 5.5.
• c) watering - 2 min - 33 ° C

method B

Like Method A, but only 25s of development time.

For the dried samples, maximum density, Gradation, sensitivity and veil determined (Table 1).

Subsequently, the samples were exposed to the light of a normalized xenon lamp and exposed to 15.0 × 10 ⁶ lx.h; thereafter, the percent density decrease was measured (Table 2).

In parallel, the same samples at 90 ° C and 50% rel. Moist 16 days stored dark and following both the percentage decrease of the maximum density as well as the Veil determined (Table 2).  

Try 2 to 7

Experiments 2 to 7 were carried out in the same way performs like experiment 1 with the difference that the color Developer P-2 in the color developer bath by equimolar Quantities of color developer P-3 (experiment 2, comparison) or inventive color developer (Experiments 3 to 7) has been replaced. The results are in the tables 1 and 2 summarized.  

The example shows that the Farbent Winder and usually for paper processing used comparison developer P-3 in the usual Development time of 45 s practically the same sensito provide metric values as the comparison developer P-2. For development times shorter than 30 s the soft with the color developers according to the invention and the Ver same developer P-3 sensitometric values obtained in contrast to those obtained with P-2 only a little from the obtained with 45 s development time. The with P-3 but obtained dyes are significantly less stable against the action of light and heat than those with the obtained color developers according to the invention, their on the other hand are as stable as those obtained with P-2.  

example 2

A color photographic recording material for color negative development was prepared (layer structure 3 in that the following layers in the given sequence to a transparent support of cellulose triacetate. Disclosures the amounts are each based on 1 m ^2. For the silver halogenidauftrag the corresponding quantities of AgNO _3. All silver halide emulsions were stabilized per 100 g of AgNO ₃ with 0.1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

3 layer structure

Layer 1 (Antihalo Layer):
black colloidal silver sol with
0.2 g Ag
1.2 g of gelatin
0.10 g UV absorber UV-2
0.20 g UV absorber UV-3
0.02 g tricresyl phosphate (TKP)
0.03 g of dibutyl phthalate (DBP)

Layer 2 (micrate intermediate layer):
Micrat silver bromide iodide emulsion (0.5 mol% iodide, mean grain diameter 0.07 μm) of 0.25 g AgNO ₃ , with
1.0 g gelatin
0.05 g red mask RM-1
0.10 g TKP

Layer 3 (1st red-sensitized layer, low sensitivity):
red sensitized silver bromide iodide emulsion (4 mol% iodide, mean grain diameter 0.45 μm) from 2.2 g AgNO ₃ , with
2.0 g of gelatin
0.6 g of cyan coupler C-19
0.05 g red mask RM-1
0.03 g of DIR coupler DIR-1
0.52 g TKP

Layer 4 (2nd red-sensitized layer, highly sensitive):
red sensitized silver bromide iodide emulsion (8.5 mol% iodide, mean grain diameter 0.8 μm) from 2.8 g AgNO ₃ , with
1.8 g of gelatin
0.15 g of cyan coupler XC-1
0.15 g DBP

Layer 5 (intermediate layer):
0.7 g of gelatin
0.2 g of 2,5-diisooctylhydroquinone
0.15 g DBP

Layer 6 (1st green sensitized layer, low sensitivity):
green-sensitized silver bromide iodide emulsion (4.5 mol% iodide, mean grain diameter 0.4 μm) from 1.8 g AgNO ₃ , with
1.6 g of gelatin
0.6 g magenta coupler XM-2
0.05 g yellow mask YM-1
0.03 g DIR coupler DIR-2
0.08 g DIR coupler DIR-3
0.11 g TKP
0.02 g DBP

Layer 7 (2nd green-sensitive layer, highly sensitive):
green-sensitized silver bromide iodide emulsion (7 mol% iodide, mean grain diameter 0.7 μm) from 2.2 g AgNO ₃ , with
1.4 g of gelatin
0.15 g magenta coupler M-12
0.03 g yellow mask YM-1
0.48 g TKP

Layer 8 (intermediate layer):
0.5 g of gelatin
0.1 g of 2,5-diisooctylhydroquinone
0.08 g DBP

Layer 9 (yellow filter layer):
yellow colloidal silver sol with
0.2 g Ag
0.9 g of gelatin
0.2 g of diisooctylhydroquinone
0.16 g DBP

Layer 10 (1st blue-sensitive layer, low sensitivity):
Blue-sensitized silver bromide iodide emulsion (4.9 mol% iodide, mean grain diameter 0.45 μm) from 0.6 g AgNO ₃ , with
0.85 g of gelatin
0.7 g yellow coupler XY-1
0.15 g DIR coupler DIR-3
0.85 g TKP

Layer 11 (2nd blue-sensitive layer, highly sensitive):
Blue-sensitized silver bromide iodide emulsion (9 mol% iodide, mean grain diameter 0.9 μm) from 1.0 g AgNO ₃ , with
0.85 g of gelatin
0.3 g yellow coupler XY-1
0.3 g TKP

Layer 12 (protective and hardening layer):
Micrat silver bromide iodide emulsion (0.5 mol% iodide, mean grain diameter 0.07 μm) from 0.5 g AgNO ₃ with
1.2 g of gelatin
0.4 g of hardener HM-2
1.0 g of formaldehyde scavenger FF

In Example 2, in addition to the already mentioned Kupp The following compounds are used:

Layer structure 4

Layer 4 was processed in the same way as layer Construction 3 made with the difference that in the Layers 6 and 7 feature the magenta couplers XM-2 and M-12 were exchanged for equimolar amounts of magenta Coupler M-23 or M-22.

Trial 8 (comparison)

Samples of the layer structures 3 and 4 were behind a Illuminated graduated gray wedge. Subsequently, the Materials with the following processing processing baths in the following manner.

• a) Color developer bath - 195 s - 37.8 ° C Diethylenetriaminepentaacetic acid | 6.6 ml potassium carbonate 32.1 g sodium 4.3 g potassium 1.5 g Kalliumiodid 1.3 g Hydroxylamine 2.1 g 4-amino-N-ethyl-N- (2-hydroxyethyl) -3-methylaniline sulfate (P-3) 4.75 g sodium 4.0 g make up to 1000 ml with water; pH 10.0.
• b) Bleaching bath - 260 s - 38 ° C Ethylenediaminetetraacetic acid (ferric ammonium salt) | 99.5 g ammonium 145 g ethylenediaminetetraacetic 2.2 g ammonium nitrate 16.3 g make up to 1000 ml with water; pH 6.0.
• c) washing - 65 s - 33 ° C
• d) Fixing bath - 260 s - 38 ° C Ammonium thiosulfate | 119 g ethylenediaminetetraacetic 1.1 g sodium 12.5 g sodium metabisulfite 1.8 g make up to 1000 ml with water; pH 7.3.
• e) watering - 200 s - 33 ° C
• f) final bath - 65 s - 33 ° C A Netzmittelhaltiges final bath with 1.2 ml Formalin to 1000 ml of water.

The samples were dried and then were Maximum density, gradation, sensitivity and fog determined (Table 3).

Thereafter, the samples at 90 ° C and 50% rel. humidity Stored dark for 16 days and then the percentage decrease in maximum density and fog determined (Table 4).

Try 9 to 14

Trials 9 through 14 were done in the same way carried out as experiment 8, except that the color developer P-3 by equimolar amounts of the color developer P-2 (Experiment 9, Comparison) or Farbent invention Winder (experiments 10 to 14) was replaced. The results These are summarized in Tables 3 and 4.  

Table 4

The example shows that the developers according to the invention not only for the processing of paper (Example 1) are suitable, but also for films. The reached sensitometric values are the same as those for Film processing commonly used comparison developers P-3 reached. Comparative developer P-2 leads to low sensitivity, gradation and maximum density. The Ent with the invention Winder formed dyes are in Heizschranklage stable.

Claims (5)

A process for producing a color photographic image by developing an exposed color photographic recording material containing at least one silver halide emulsion layer in the presence of a color coupler and a color developing agent, characterized in that the color developing agent used is a compound of the formula I or salts thereof in which mean
R ^{1 is} alkyl or alkoxy;
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ H, -OH, -COOH, -SO ₃ H, alkyl, aryl, acyl, alkoxy, aryloxy, acyloxy, alkyl thio, sulfinyl, sulfonyl, sulfamoyl , Acylamino, sulfonamido,
wherein at least one of R ² to R ^{7 is} different from H;
m, n is 0 or 1. 2. The method according to claim 1, characterized that the color photographic recording material at least one blue-sensitive yellow coupler a silver halide emulsion layer, a green sensitive magenta coupler containing silver halo nidemulsionsschicht and a red-sensitive cyan coupler-containing silver halide emulsion layer has, in the specified sequence, given if necessary by non-photosensitive intermediate layers separated, on a light-reflecting or transparent substrate are arranged. 3. The method according to claim 2, characterized that the silver halide to at least 98 mol% of Silver chloride exists and that the duration of the color development is less than 35 s. 4. Compound of formula I in which mean
R ^{1 is} alkyl or alkoxy;
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ H, -OH, -COOH, -SO ₃ H, alkyl, aryl, acyl, alkoxy, aryloxy, acyloxy, alkylthio, sulfinyl, sulfonyl, sulfamoyl, Acylamino, sulfonamido, wherein at least one of R ² to R ^{7 is} different from H;
m, n is 0 or 1. 5. A compound of the formula I (according to claim 4), characterized in that a by R ² to R ⁷ Darge presented or contained therein alkyl, alkoxy or aryl group is substituted with a polar, the solubility in an aqueous medium-promoting group.