DE4009181A1 - COLOR PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL AND ITS DEVELOPMENT - Google Patents

Description

The invention relates to a color photographic silver halide material, by a small amount of silver halide on the one hand and certain silver halide emulsions on the other hand is characterized. Farther The invention relates to a development process for the The aforesaid material in which a combined Influence of developer and H₂O₂ is performed.

Usual silver halide materials for the production of Color supervisors included on a reflective Carrier each a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer, in the order given yellow coupler, magenta coupler and cyan couplers are assigned. Farther contain these materials usual intermediate and Protective layers. To be at exposure and development by coupling the color couplers with the developer oxidation product to achieve sufficient color density  certain minimum amounts of silver halides are required, on the other hand also for sufficient Sensitivity during the copying process. About all 3 Color densities are currently reported as silver halide levels as AgNO₃, of at least 1 g / m² in use.

With the development, a corresponding one is created in addition to the color image Silver image that is clear and to the colors shining forth, must be removed. This happens in the following on the development Silver removal step, which consists of bleaching steps and fixing exists. The processing method becomes completed by watering or stabilizing and drying.

To lower the silver order is already proposed been developing with a reinforcing method to combine in which a H₂O₂-containing Reinforcement solution on the only weakly developed Color image acts and this reinforced so much that the usual color densities arise. This procedure is until now not put into practice, because the desired results in continuous operation not reached or extensive measures have been taken had to remove interfering bromide and iodide ions from the reinforcing baths keep away, for example by the Use of ion exchangers (DE-A 25 27 398, DE-A 32 28 192, DE-A 33 02 741, US-A 43 71 609, US-A 45 29 687).  

In the methods proposed so far, silver chloride bromide emulsions have been used with at least 30 mole percent bromide and silver bromide iodide emulsion having high bromide contents used. Also proposed were 100% Silberchloridemulsionen, however, when reworked yielded insufficient results.

Object of the present invention was such Reinforcement process and a suitable material Find images that are easy and safe enough images Quality will be preserved.

The invention relates to a color photographic recording material with at least one blue-sensitive, at least one yellow coupler-containing silver halide emulsion layer, at least one green sensitive, at least one magenta-containing silver halide emulsion layer and at least one red-sensitive, at least one cyan coupler containing Silver halide emulsion layer and conventional Intermediate and protective layers, characterized that the silver halide order of all photosensitive Layers, reported as AgNO₃, not more than 0.3 g / m² is and in at least one photosensitive Layer as emulsion a silver chloride bromide emulsion with 0.1 to 3 mol% of silver bromide is used. Preferably At least 50% of silver bromide is present on the surface of the silver halide grains. Such Emulsions are obtained in particular by the fact that AgCl emulsions and AgClBr emulsions with lower Bromide content as desired after sensitization with the aqueous solution of a bromide treated.  

Preferably, the emulsions are all photosensitive Layers of AgClBr emulsions of the type mentioned, wherein the Bromidanteile within the inserted frame may differ from one layer to another.

Preferably, the silver halides have a bromide content from 0.2 to 2 mol%.

In addition, the silver halide grains can be up to Containing 0.5 mol% of silver iodide, but are preferably silver iodide.

The color photographic recording material is preferably from a reflective support, on the in the specified order a blue-sensitive, at least a yellow coupler containing layer, a green sensitive, containing at least one magenta coupler Layer and a red-sensitive, at least one Cyan coupler containing layer and conventional Intermediate and protective layers are applied.

The silver halide order, given as AgNO₃ is preferably 0.05 to 0.2 g / m².

Another object of the invention is a development process for the above material after imagewise exposure, the material with a Color developer of p-phenylenediamine series and aqueous H₂O₂ is treated.

Development can be one-bath or two-bath, preferably the concentrations of color developer 0.01 to 0.1 mol / l and H₂O₂ be 0.5 to 25 g / l.  

The development and reinforcement can become the usual Steps bleaching, fixing, watering and drying, Whitening and fixing in a bath can be performed (Bleachfixierbad). A special Advantage of the method is, however, that the small amount of silver halide is so weak Silver image creates that the color image does not bother and therefore does not need to be removed. The bleaching can thus be omitted. Also the fixing (releasing the unexposed Silver halide) may be omitted if the Silver halide through a stabilizer in a light-insensitive Silver Complex salt is transferred. In This case can be stabilized immediately Connect drying.

In addition to the silver halide grains and the color couplers contain the silver halide emulsion layers in essentially a binder, which is also more important Part of the intermediate and protective layers is.

The binder used is preferably gelatin. However, this can be done in whole or in part by others synthetic, semi-synthetic or naturally occurring Be replaced polymers. Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, Polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are 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 hydroxyalkyl cellulose,  Carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives obtained by reaction with alkylating or acylating agents or by Grafting of polymerizable monomers obtained are 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 especially amino groups, but also Carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin preferably used can be acidic or alkaline digestion. It can also oxidized gelatin can be used. The production Such gelatins are described, for example, in The Science and Technology of Gelatine, edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 et seq. The gelatine used should be as possible low content of photographically active impurities contained (inert gelatin). Gelatins with high viscosity and low swelling are special advantageous.

In the silver halides used in the invention they can be mostly compact crystals, the z. B. are regular cubic or octahedral or May have transitional forms. The silver halo may also be present as platelet-shaped crystals,  their average ratio of diameter to Thickness z. B. at least 5: 1, wherein the diameter a grain is defined as the diameter of a grain Circle with a circle content corresponding to the projected Area of the grain. But the layers can also have tabular silver halide crystals, where the ratio of diameter to thickness is significantly greater than 5: 1, z. From 12: 1 to 30: 1.

The mean grain size of the emulsions is preferably between 0.2 μm and 2.0 μm, the particle size distribution may be both homo- and heterodisperse. homodisperse Grain size distribution means that 95% of the grains not more than ± 30% of the mean grain size. Homodisperse silver halide emulsions are preferred. The emulsions may be in addition to the silver halide also contain organic silver salts, for. B. silver benzotriazolate or silver behenate.

Two or more kinds of silver halide emulsions, which are prepared separately, as a mixture be used.

The photographic emulsions can be different Methods (eg, P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al., Making and Coating Photographic Emulsion, The Focal Press (1966) soluble silver salts and soluble halides become.  

The precipitation of the silver halide is preferably carried out in Presence of the binder, e.g. As the gelatin and can carried out in acidic, neutral or alkaline pH range preferably silver halide complexing agents additionally used. To the latter belong z. As ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The merge the water-soluble silver salts and the halides takes place one after the other after the single-jet or simultaneously using the double-jet method or by any combination of both methods. Prefers is the dosage with increasing inflow rates, the "critical" feed rate at which just no new germs arise, not exceeded should be. The pAg area may be during the Precipitation vary within wide limits, preferably the so-called pAg-controlled process is used, in which a certain pAg value is kept constant or traversing a defined pAg profile during the precipitation becomes. In addition to the preferred precipitation with halide excess but is also the so-called inverse Precipitation possible with silver ion excess. Except by Precipitation can also be done by the silver halide crystals Physical maturation (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent to grow. The growth of the emulsion grains can even be overwhelmingly due to Ostwald ripening take place, preferably a fine-grained, so-called Lippmann emulsion, with a sparingly soluble Emulsion is mixed and redissolved on the latter.  

During precipitation and / or physical ripening The silver halide grains may also be salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe to be available.

Furthermore, the precipitation may also be in the presence of sensitizing dyes respectively. complexing and / or dyes can be added to any Make ineffective, eg. B. by changing the pH or by an oxidative treatment.

After completed crystal formation or already too earlier, the soluble salts were off the emulsion removed, z. By noodles and washing, by flocculation and washing, by ultrafiltration or by ion exchanger.

The silver halide emulsion generally becomes one chemical senibilization under defined conditions pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until it reaches subjected to the sensitivity and fog optimum. The procedure is. z. B. in H. Frieser "The basics Photographic Processes with Silver Halides " Page 675-734, Academic Publishing Company (1968).

In this case, the chemical sensitization with addition of compounds of sulfur, selenium, tellurium and / or Compounds of the metals of the VIII. Subgroup of Periodic table (eg gold, platinum, palladium, iridium)  Thiocyanatverbindungen, surface-active Compounds such as thioether, heterocyclic Nitrogen compounds (eg imidazoles, azaindenes) or also spectral sensitizers (described, for example, in US Pat. F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Vol. 18, p. 431 ff. And Research Disclosure 17 643 (Dec. 1978), Chapter III) are added. Alternatively, or additionally, a reduction sensitization with the addition of reducing agents (stannous salts, Amines, hydrazine derivatives, aminoboranes, silanes, Formamidinsulfinsäure) by hydrogen, by low pAg (eg less than 5) and / or high pH (eg over 8).

The photographic emulsions may be compounds for Prevention of fogging or stabilization the photographic function during production, the Storage or photographic processing included.

Particularly suitable are azaindenes, preferably tetracenes and pentaazaindenes, especially those with Hydroxyl or amino groups are substituted. such Connections are z. B. von Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Next can as Antifogg salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as Benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted Benzotriazoles or Benzthiazoliumsalze used  become. Also suitable are mercapto groups containing heterocycles, eg. Mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, Mercaptopyrimidines, these mercaptoazoles also a water-solubilizing group, e.g. B. a carboxyl group or sulfo group. Further suitable compounds are described in Research Disclosure 17643 (Dec., 1978), Chapter VI.

The stabilizers can be added to the silver halide emulsions be added before, during or after their maturation. Of course you can do the connections to others photographic layers containing a silver halide layer are assigned, enforce.

It is also possible to use mixtures of two or more of these Connections are used.

The photographic emulsion layers or other hydrophilic Colloid layers of the invention produced Photosensitive material can be surface-active Containing agents for various purposes, such as coating aids, to prevent electrical charging, to Improvement, the anti-slip properties, to emulsify the Dispersion, to prevent adhesion and to improve it the photographic characteristics (eg development acceleration, high contrast, sensitization etc.). In addition to natural surface-active compounds, z. As saponin, find mainly synthetic Surface-active compounds (surfactants) Use:  nonionic surfactants, e.g. For example, alkylene oxide compounds, Glycerol compounds or glycidol compounds, cationic Surfactants, e.g. B. higher alkylamines, quaternary ammonium salts, Pyridine compounds and other heterocyclic Compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing one Acid group, eg. Carboxylic acid, sulfonic acid, a phosphoric acid, Sulfuric ester or phosphoric ester group, ampholytic surfactants, e.g. B. amino acid and Aminosulfonsäureverbindungen and sulfuric or phosphoric acid esters an aminoalcohol. Are also suitable fluorine-containing surfactants, the z. B. from GB-PS 13 30 356, 15 24 631 and US-PS 36 66 478 and 36 89 906 known are.

The photographic emulsions can be made using of methine dyes or other dyes spectrally be sensitized. Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex ones Merocyanine.

An overview of those suitable as spectral sensitizers Polymethine dyes, their suitable combinations and supersensitizing combinations contains Research Disclosure 17 643 (Dec. 1978), chapters IV.

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

1. as red sensitizers

9-Ethylcarbocyanine with benzothiazole, Benzelenazole 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 -selencarbocyanine and 9-ethyl-naphthothiaoxa or benzimidazocarbocyanines, provided that the dyes at least one sulfoalkyl group on the heterocyclic Carry 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 also at least one sulfoalkyl group on the heterocyclic Contain nitrogen.

3. as blue sensitizers

Symmetrical or asymmetric benzimidazo, oxa, Thia- or selenocyanines with at least one Sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on the aromatic Kern, as well as Apomerocyanine with a Rhodanin group.  

Color coupler for producing the cyan partial color image are usually phenol or α-naphthol type couplers; Color coupler for the production of crimson Part color image are usually couplers of the type 5-pyrazolone, indazolone or pyrazoloazole; Color coupler for producing the yellow partial color image are usually couplers with an open-chain ketomethylene grouping, in particular of the benzoylacetanilide type and the α-pivaloylacetanilides. examples for the couplers are numerous described in the literature. The couplers may also be of high molecular weight, so-called Latex coupler.

High molecular color couplers are described, for example, in DE-C-12 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-40 80 211 described. The high molecular color couplers are in usually by polymerization of ethylenically unsaturated produced monomeric color couplers. You can but also obtained by polyaddition or polycondensation become.

The incorporation of the couplers or other compounds in silver halide emulsion layers can in the way be done first by the relevant connection prepared a solution, a dispersion or an emulsion and then the casting solution for that particular Layer is added. The selection of the appropriate Solvent or dispersant depends on the particular Solubility of the compound.  

Methods for introducing into water substantially insoluble compounds by grinding processes are for example in DE-A-26 09 741 and DE-A-26 09 742 described.

Hydrophobic compounds can also be made using high-boiling solvents, so-called oil formers, be introduced into the casting solution. Appropriate methods are for example in US-A-23 22 027, US-A-28 01 170, US-A-28 01 171 and EP-A-00 43 037.

Instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers use Find.

The compounds may also be in the form of loaded latices be introduced into the casting solution. Is referred for example, DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-A-00 14 921, EP-A-00 69 671, EP-A-01 30 115, US-A-42 91 113.

The diffusion-resistant inclusion of anionic water-soluble Compounds (eg of dyes) can also be used with Help of cationic polymers, so-called pickle polymers respectively.

Suitable oil formers are z. Phthalic acid alkyl ester, Phosphonic acid esters, phosphoric acid esters, citric acid esters, Benzoic acid esters, amides, fatty acid esters, trimesic acid esters, Alcohols, phenols, aniline derivatives and Hydrocarbons.  

Examples of suitable oil formers are dibutyl phthalate, Dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, Tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, Tridecyl phosphate, tributoxyethyl phosphate, Trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate, Diethyldodecanmide, N-tetradecylpyrrolidone, Isostearyl alcohol, 2,4-di-t-amylphenol, Dioctyl acelate, glycerol tributyrate, isostearyl lactate, Trioctyl citrate, N, N-dibutyl-2-butoxy-5-t-octylaniline, Paraffin, dodecylbenzene and diisopropylnaphthalene.

Each of the differently sensitized, photosensitive Layers can consist of a single layer or also two or more silver halide emulsion partial layers include.

The usually between layers of different Spectral sensitivity arranged non-photosensitive 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 as well as in EP-A-00 69 070, 00 98 072, 01 24 877, 01 25 522 described.

The photographic material may further comprise UV-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, dye, coupler and whitener stabilizer additives, color fog reducing agents, plasticizers (latices), Biocide and other included.

UV-absorbing compounds are said to be the image dyes before fading due to UV-rich daylight protect. Usually, for the two tasks Compounds of different structure used. Examples are aryl-substituted benzotriazole compounds (US-A-35 33 794), 4-thiazolidone compounds (US-A-33 14 794 and 33 52 681), benzophenone compounds (JP-A-2784/71), Cinnamic acid ester compounds (US-A-37 05 805 and 37 07 375), butadiene compounds (US Pat. No. 4,045,229) or benzoxazole compounds (US Pat. No. 3,700,455).

Particularly suitable UV absorbers should light up to Absorb 400 nm and in their light absorption capacity fall steeply at wavelengths above 400 nm.  

Examples of particularly suitable compounds

R, R¹ = H; R² = -C₄H₉-t
R = H; R¹, R² = -C₄H₉-t
R = H; R¹, R² = -C₅H₁₁-t
R = H; R¹ = -C₄H₉-s; R² = -C₄H₉-t
R = Cl; R¹ = -C₄H₉-t; R² = -C₄H₉-s
R = Cl; R¹, R² = -C₄H₉-t
R = Cl; R¹ = -C₄H₉-t; R² = -CH₂-CH₂-COOC₈H₁₇
R = H; R = -C₁₂H₂₅-i; R² = -CH₃
R, R¹, R² = -C₄H₉-t

R¹, R² = -C₆H₁₃-n; R³, R⁴ = -CN
R¹, R² = -C₂H₅;

R⁴ = -CO-OC₈H₁₇
R¹, R² = -C₂H₅;

R⁴ = -COO-C₁₂H₂₅
R¹, R² = -CH₂ = CH-CH₂; R³, R⁴ = -CN

R1, R2 = H; R3 = -CN; R⁴ = -CO-NHC₁₂H₂₅
R¹, R² = -CH₃; R3 = -CN; R⁴ = -CO-NHC₁₂H₂₅

For visible light suitable filter dyes include Oxonol dyes, hemioxonol dyes, styryl dyes, Merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, Hemioxonol dyes and merocyanine dyes used particularly advantageous.

Suitable whiteners are z. In Research Disclosure 17,643 (Dec., 1978), Chapter V, in US-A-26 32 701, 32 69 840 and in GB-A-8 52 075 and 13 19 763 described.  

Certain binder layers, in particular those of Wearer furthest away, but also occasionally Interlayers, especially if they are during production the furthest from the wearer represent distant layer, can photographically inert Contain particles of inorganic or organic nature, z. B. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).

The mean particle diameter of the spacers is in particular in the range of 0.2 to 10 microns. The spacers are insoluble in water and can be alkali-insoluble or alkali-soluble, the alkali-soluble generally in the alkaline development bath removed from the photographic material. Examples suitable polymers include polymethylmethacrylate, copolymers from acrylic acid and methyl methacrylate as well Hydroxypropylmethyl cellulose.

Additives to improve the dye, coupler and White stability and to reduce color fog (Research Disclosure 17 643 (Dec., 1978), Chapter VII) may belong to the following chemical classes: Hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, Spirochromans, spiroindans, p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, Methylenedioxybenzenes, aminophenols, sterically hindered Amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.  

Compounds, they have both a sterically hindered amine partial structure as well as a sterically hindered one Phenol partial structure in one molecule (US-A-42 68 593), are particularly effective for prevention the impairment of yellow color images as a result the development of heat, moisture and light. Around the impairment of purple color images, in particular their impairment as a result of exposure of light to prevent are spiroindanes (JP-A-1 59 644/81) and chromans produced by hydroquinone diethers or monoethers are substituted (JP-A-89 835/80) especially effective.

The layers of photographic material can with hardened the usual curing agents. suitable Hardeners are z. As formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis- (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and others Compounds containing reactive halogen (US-A-32 88 775, US-A-27 32 303, GB-A-9 74 723 and GB-A-11 67 207), Divinylsulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine and other connections, which contain a reactive olefin bond (US Pat. No. 3,635,718, US-A-32 32 763 and GB-A-9 94 869); N-hydroxymethyl phthalimide and other N-methylol compounds (US Pat. No. 2,732,316 and US-A-2586168); Isocyanates (US Pat. No. 3,903,437); Aziridine compounds (US-A-3,017,280 and US-A-2,983,611); Acid derivatives (US-A-2,725,294 and US-A-2,725,295); Carbodiimide type compounds (US-A-31 00 704); Carbamoylpyridiniumsalze (DE-A-22 25 230 and  DE-A-24 39 551); Carbamoyl oxypyridinium compounds (DE-A-24 08 814); Compounds with a phosphorus-halogen bond (JP-A-1 13 929/83); N-Carbonyloximid compounds (JP-A-43353/81); N-sulfonyloximido compounds (US Pat. No. 4,111,926), Dihydroquinoline compounds (US Pat. No. 4,013,468), 2-sulfonyloxypyridinium salts (JP-A-1 10 762/81), Formamidinium salts (EP-A-01 62 308), compounds with two or more N-acyloximino groups (US Pat. No. 4,052,373), Epoxy compounds (US Pat. No. 3,091,537), Isoxazole-type compounds (US-A-33 21 313 and US-A-35 43 292); Halogencarboxyaldehyde, such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate.

The curing can be effected in a known manner by that the curing agent of the casting solution for the hardening layer is added, or in that the to be hardened layer with a layer overcoated which contains a diffusible curing agent.

Among the listed classes, there are slow-acting ones and fast-acting hardeners and so-called Instant hardeners that are particularly beneficial. Under Emergency workers are understood to be compounds which are suitable Crosslink the binder so that immediately after Beguß, at the latest after 24 hours, preferably Hardening completed at the latest after 8 hours is that no further by the Venetzungsreaktion conditional change of the sensitometry and the  Swelling of the layer dressing occurs. Under swelling is the difference between wet film thickness and dry film thickness in the aqueous processing of the film (Photograph Sci., Eng. 8 (1964), 275; Sci. Closely. (1972), 499).

In these with gelatin very fast reacting hardeners is it z. Carbamoylpyridinium salts, those with free carboxyl groups of gelatin react, so that the latter with free amino groups gelatin to form peptide bonds and crosslinking of the gelatin.

Suitable examples of instant hardeners are e.g. B. compounds the general formulas

wherein
R 1 is alkyl, aryl or aralkyl,
R 2 has the same meaning as R 1 or is alkylene, arylene, aralkylene or Alkaralkylen, wherein the second bond with a group of the formula

linked, or
R¹ and R² together represent the necessary to complete an optionally substituted heterocyclic ring, such as a piperidine, piperazine or morpholine ring atoms required, wherein the ring z. B. may be substituted by C₁-C₃-alkyl or halogen,
R³ is hydrogen, alkyl, aryl, alkoxy, -NR⁴-COR⁵, - (CH₂) _m -NR⁸R⁹, - (CH₂) _n -CONR¹³R¹⁴ or

or a bridge member or a direct bond to a polymer chain, wherein
R⁴, R⁶, R⁷, R⁹, R¹⁴, R¹⁵, R¹⁷, R¹⁸ and R¹⁹ are hydrogen or C₁-C₄-alkyl,
R⁵ is hydrogen, C₁-C₄-alkyl or NR⁶R⁷,
R⁸ -COR¹⁰,
R¹⁰ NR¹¹R¹²,
R¹¹ is C₁-C₄-alkyl or aryl, in particular phenyl,
R¹² is hydrogen, C₁-C₄-alkyl or aryl, in particular phenyl,
R¹³ is hydrogen, C₁-C₄-alkyl or aryl, in particular phenyl,
R¹⁶ is hydrogen, C₁-C₄-alkyl, -COR¹⁸ or -CONHR¹⁹,
m is a number 1 to 3,
n is a number 0 to 3,
p is a number 2 to 3 and
Mean YO or NR¹⁷ or
R¹³ and R¹⁴ together represent the necessary for the completion of an optionally substituted heterocyclic ring, such as a piperidine, piperazine or morpholine ring atoms, wherein the ring z. B. may be substituted by C₁-C₃-alkyl or halogen,
Z for the completion of a 5- or 6-membered aromatic heterocyclic ring, optionally with fused benzene ring, C atoms required and
X⊖ represents an anion, which is omitted if an anionic group is already linked to the rest of the molecule;

wherein
R¹, R², R³ and X⊖ have the meaning given for formula (a).

There are diffusible curing agents that work on everyone Layers within a layer structure in the same Way hardening act. But there are also stratum-limited acting, non-diffusing, low molecular weight and high molecular weight hardener. With them you can individual Layers, z. B. crosslink the protective layer particularly strong. This is important when considering the silver halide layer because of the Silberdeckkrafterhöhung little hardens and with the protective layer the mechanical properties must improve (EP-A-01 14 699).

As the color developer compound, all Developer compounds use the ability in the form of their oxidation product with color couplers to azomethine or indophenol dyes react. Suitable color developing agents are aromatic, containing at least one primary amino group P-Phenylenediamine type compounds, for example N, N-dialkyl-p-phenylenediamines such as N, N-  Diethyl p-phenylenediamine, 1- (N-ethyl-N-methanesulfone amidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N- hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl) N-methoxyethyl) -3-methyl-p-phenylenediamine. Further useful color developers are described, 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 et seq.

The treatment with aqueous H₂O₂ can simultaneously or following the development.

After the color development and the H₂O₂ treatment can an acid stop bath or a watering as well as bleaching and fixing, with bleaching and fixing, especially because of the small amounts of silver that are formed be bleached. The Fixation can be replaced by stabilization.

As a bleaching agent z. As Fe (III) salts and Fe (III) complex salts such as ferricyanide, dichromate, water-soluble Cobalt complexes are used. Especially preferred are iron (III) complexes of aminopolycarboxylic acids, in particular z. From ethylenediaminetetraacetic acid, Propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, Nitrilotriacetic acid, iminodiacetic acid, N- Hydroxyethyl-ethylenediaminetriacetic acid, Alkyliminodicarbonsäuren and of corresponding phosphonic acids. suitable as bleaching agents are persulfates and Peroxides, e.g. B. hydrogen peroxide.  

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

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

However, the watering can be complete by a stabilizer be replaced, usually in countercurrent to be led. This stabilizer bath takes over with formaldehyde addition also the function of a final bath.

Preparation of the emulsions

A monodisperse silver chloride emulsion of 0.8 micron average grain diameter was prepared by double inlet of an AgNO₃ and NaCl solution containing Na₄IrCl₆ prepared. The Ir content was 0.05 × 10 ^-6 mol / mol Ag. The emulsion was flocculated in the usual manner, washed and redispersed with gelatin. The weight ratio gelatin-silver (as AgNO₃) was 0.5. The content of AgCl was 1 mole per kg of emulsion.

Subsequently, the emulsion was matured with 20 × 10 ^-6 mol of thiosulfate and 2 × 10 ^-6 mol of AuCl₄ per mol of Ag for optimum sensitivity. After completion of the ripening, the emulsion was sensitized with blue sensitizer BS 1 (400 × 10 ^-6 mol / mol Ag) for the blue spectral region and then stabilized with stabilizer ST 1 (243 × 10 ^-6 mol / mol Ag).

This starting emulsion was KBr solution in different Quantities added, in each case based on Total silver:

mol% EM 1 0 EM 2 0.5 EM 3 1 EM 4 2 EM 5 5 EM 6 10

Emulsion 7

According to EM 2, a green-sensitive emulsion was formed with 99.5 mole% chloride, 0.5 mole% bromide and a average grain diameter of 0.4 microns produced (EM 7).

Emulsion 8

According to EM 2, a red-sensitive emulsion with 99.5 mole% chloride, 0.5 mole% bromide and a grain diameter 0.35 μm (E, 8).

example 1

A color photographic recording material was made by placing on a substrate of both sides polyethylene coated paper the following Layers applied in the order given were. The quantities refer to each on 1 m². For the silver halide order, the corresponding Amounts indicated AgNO₃

Layer structure 1

1st layer (substrate layer):
0.3 g of gelatin
2nd layer (blue-sensitive layer):
0.08 g of AgNO₃ EM 1
1.0 g gelatin
0.6 g yellow coupler GB 1
0.48 g tricresyl phosphate
3rd layer (protective layer):
1.1 g of gelatin
0.06 g of 2,5-dioctylhydroquinone
0.06 g of dibutyl phthalate
4th layer (green-sensitive layer):
0.05 g of AgNO₃ EM 7
1.08 g of gelatin
0.4 g of magenta coupler PP 1
0.43 g of tricresyl phosphate
5th layer (UV protection layer):
1.3 g of gelatin
0.56 g UV absorber UV 1
0.3 g tricresyl phosphate
6th layer (red-sensitive layer):
0.05 g of AgNO₃ EM 8
0.70 g of gelatin
0.38 g cyan coupler BG 1
0.38 g of tricresyl phosphate
7th layer (UV protection layer):
0.60 g of gelatin
0.2 g UV absorber UV 1
0.1 g tricresyl phosphate
8th layer (hardener layer):
0.9 g of gelatin
0.2 g of hardener H 1

Example 2 to 6

There were further layer structures produced by in layer 2 in each case 0.08 g of AgNO₃ EM 2 to EM 6 used were.

The layer structures of Examples 1 produced in this way to 6 were imagewise exposed by a sensitometer and developed as follows:

Since the amount of silver developed was very small, was waived on a bleaching stage.

Color developer solution

Polyglycol P 400 22 ml
Diethyl-hydroxylamine (85% by weight) 6 ml
CD 3 10 g
Potassium sulfite 0.33 g
1-hydroxyethane-1,1-diphosphonic acid 0.14 g
Potassium hydrogen carbonate 5 g
Potassium carbonate 22 g
Potassium hydroxide 8 g
Dodecylbenzenesulfonate 0.02 g
Methylbenzotriazole 0.005 g
make up to 1000 ml with water; pH 10.6

intensifying bath

Aqueous hydrogen peroxide 0.5 wt .-% with KOH to pH 7,0.

fixing

Ammonium thiosulfate 50 g
Sodium sulfite 5 g
Sodium hydrogen sulfite 2 g
make up to 1000 ml with water; pH 6.0

The processed and dried samples were behind Blue, green and red filters measured. From the Measurement results (Table 1) can be seen that, firstly without Bromidanteil while a sufficient maximum density but only achieved unsatisfactory sensitivity secondly, that is the range of favorable bromide content in the emulsion is very narrow, and that outside of this area in a layer also the other photosensitive layers negatively affected become.

Examples 7 to 12

The layer structures 1-6 were with the change that the blue-sensitive emulsion each 0.4 mg / m² 5-butylbenzotriazole were added, repeated. These Layer structures 7-12 were also replaced by a Sensitometer exposed and developed as follows:  

Developer-amplifier solution

Polyglycol P 400 22 ml
Diethyl-hydroxylamine (85% by weight) 6 ml
CD 3 10 g
Potassium sulfite 0.33 g
1-hydroxyethane-1,1-diphosphonic acid 0.14 g
Potassium hydrogen carbonate 5 g
Potassium carbonate 22 g
Potassium hydroxide 8 g
Dodecylbenzenesulfonate 0.02 g
Hydrogen peroxide 35% strength by weight 10 ml
make up to 1000 ml with water; pH 10.6

The measurement results shown in Table 2 demonstrate that even with the use of a one-part developer enhancer solution, the effect of bromide content of the emulsion is critical to the performance of the enhancement process.

Claims (10)

A color photographic recording material comprising at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive, at least one magenta silver halide emulsion layer and at least one red-sensitive, at least cyan coupler containing silver halide emulsion layer and conventional intermediate and protective layers, characterized in that the silver halide coating of all photosensitive layers , as AgNO₃, is not more than 0.3 g / m², and in at least one photosensitive layer, a silver chloride bromide emulsion containing 0.1 to 3 mol% of silver bromide is used as an emulsion. 2. Color photographic recording material according to claim 1, wherein at least 50% of the silver bromide on the surface of the silver halide grains are located. 3. Color photographic recording material according to claim 1, characterized in that the silver bromide content 0.2 to 2 mol% and the Silver halide emulsion is iodide-free.   4.color photographic recording material according to claim 1, characterized in that the Emulsions of all photosensitive layers AgClBr emulsions containing 0.1 to 3 mol% silver bromide are. 5. color photographic recording material according to claim 4, characterized in that the Bromidanteile on the silver chlorobromides of the individual Photosensitive layers are different. 6. color photographic recording material according to claim 1, characterized in that the silver halide coating, given as AgNO₃, 0.05 to 0.2 g / m². 7. Color photographic development process, thereby characterized in that a imagewise exposed material according to claim 1 a color development and a gain with H₂O₂ is subjected. 8. The method according to claim 7, characterized that with a color developer of the p-phenylenediamine series in a concentration of 0.01 to 0.1 mol / l and an amplifier solution of 0.5 to 25 g H₂O₂ / l is developed. 9. The method according to claim 7, characterized that development and reinforcement in one operation be performed.   10. A process for the production of color images from a Color photographic recording material according to Claim 1 by developing and amplifying according to Claim 7, fixing, watering and drying, in which no bleaching occurs.