DE3730557A1 - Process for the production of colour photographs (prints), and colour-photographic recording material suitable for this purpose - Google Patents

Abstract

A colour-photographic recording material having at least one photosensitive silver-halide emulsion layer associated with a diequivalent magenta coupler of formula I and an oil former of formula II allows the production, in a short processing process, of colour photographs of high colour density whose colour balance is not significantly changed during processing. <IMAGE> n is from 1 to 5; m is from 1 to 3; X i a removalable group of the formula -S-R<3>; R<1> is halogen, alkoxy, alkylthio, acylamino, sulfamoyl or alkoxycarbonyl; R<2> is halogen, cyano, thiocyanato, alkoxy, alkyl, acylamino or alkoxycarbonyl; R<3> is alkyl, aryl or a heterocyclic group; <IMAGE> R<4> is alkyl; R<5> is alkyl; R<6> is alkyl or <IMAGE> or R<4> and R<5> together or R<4> and R<6> together are the radical for completion of a 5- or 6-membered heterocyclic ring; R<7> is alkylene or arylene p is 0 or 1. li

Description

The invention relates to a process for the preparation colored pictures, in which an imagewise exposed color photographic recording material with at least a photosensitive silver halide emulsion layer, which is a 2-equivalent magenta coupler from pyrazolone Type and a specific oil former are assigned, a short-term processing process is subjected. Of Furthermore, the invention relates to a particular for this purpose suitable color photographic recording material.

It is known, color photographic images by chromogenic Development, d. H. by having one imagewise exposed recording material with at least a silver halide emulsion layer in the presence suitable color coupler by means of suitable color-forming Develops developing substances, which in accordance with the silver image resulting oxidation product the developer substances with the color coupler below Formation of a dye image reacts.  

As magenta coupler, d. H. as a color coupler used to generate of the purple color image are suitable in the general compounds which differ from the pyrazolone Derive 5. Common magenta couplers are, for example Pyrazolone-5 compounds in the 3-position are substituted by an acylamino group. This opposite 3-anilinopyrazolone-5 couplers are known low secondary densities in both red and blue Spectral range, by heating, tropical and storage cabinet stability, by excellent light stability with the azomethine dyes formed from p-phenylenediamines and due to high reactivity and coupling activity.

To improve the effectiveness of color formation were Used 2-equivalent magenta couplers in which a substituent in the coupling position of the purple coupler from Pyrazolone type introduced and in color development than Leaving group is split off. Such couplers are For example, in US-A 33 11 476, 34 19 391, 36 17 291 and 39 26 631 and in DE-A 25 36 191, 26 51 363 and 27 03 589 described. Other magenta couplers in which a substituent, in particular an aryl radical, to which Coupling position is bound by a sulfur atom, are described in US-A 32 14 437, 40 32 346, 32 27 554, 37 01 783 and 43 83 027, in EP-A 00 81 768 in JA 34 044/78 and in DE-A 29 44 601 and 33 18 759 described.

Such 2-equivalent couplers couple during normal processing with a sufficiently high color formation rate, which  in the sense of saving silver and coupler has a favorable effect.

Extensive research has shown that the Speed of color formation reaction that occurs in the present case of addition of oxidized color developer and eliminating a fugitive group, significantly lower than when using 4-equivalent couplers, which involved the addition of oxidized Color developers a (further) oxidation reaction followed. With shortened processing this leads in the case of using 2-equivalent magenta couplers to the undesirable result, that after some Time after completion of processing the full color density can be obtained, but on the other hand immediately at the completion of the processing, the color formation is still incomplete is what makes the assessment extremely difficult.

The invention is based on the object for the short-term processing method a color photographic recording material specify with the immediately after the processing obtained color images with high color density whose color coordination is completed the processing no longer changes significantly. At the same time all advantages of 2-equivalent couplers remain.

The invention relates to a process for the preparation colored pictures, in which an imagewise exposed,  color photographic recording material with at least a photosensitive silver halide emulsion layer, a 2-equivalent pyrazolone type coupler and an oil former, a short-term processing process is subjected, characterized that the 2-equivalent magenta coupler of the following Formula I corresponds

in which mean
n 1 to 5;
m 1 to 3;
X is a leaving group of the formula -S-R³;
R¹ is halogen, alkoxy, alkylthio, acylamino, sulfamoyl or alkoxycarbonyl;
R 2 is halogen, cyano, thiocyanato, alkoxy, alkyl, acylamino, alkoxycarbonyl;
R 3 is alkyl, aryl or a heterocyclic group;
and that an amide compound of the general formula II is used as the oil former

in which mean
R⁴ alkyl;
R⁵ alkyl;

or R⁴ and R⁵ together or R⁴ and R⁶ together form the radical to complete a 5- or 6-membered heterocyclic ring;
R⁷ is alkylene or arylene;
p 0 or 1.

A halogen atom represented by R 1 or R 2 in formula I is preferably Cl. An alkoxy or alkylthio radical can contain 1 to 18 C atoms. Examples are -OCH₃, -OC₄H₉, -OC₈H₁₇ and -S-C₁₄H₂₉. An acyl group contained in an acylamino group may be derived from an aliphatic or aromatic carboxylic acid or sulfonic acid, a carbamic acid, a sulfamic acid or a carbonic acid half ester. The aliphatic portion of a carbamoyl, sulfamoyl or alkoxycarbonyl group may comprise up to 18 carbon atoms and be optionally substituted. If m or n is greater than 1, the multiple radicals R 1 and R 2, respectively, do not necessarily have to be identical. The couplers of the formula I preferably contain a pronounced radical B at some point in the molecule, which owing to its size and structure gives the coupler sufficient diffusion resistance and, moreover, can have stabilizing properties. Examples of such radicals are given below:

The leaving group X is preferably the radical of an aliphatic or aromatic mercaptan. Examples of such radicals are listed in the following table:

Radicals of the general formula

wherein
Ra alkyl or aryl,
Y is alkyl or alkoxy and
k is 1 or 2,
are particularly preferred as cleavable group X.

For example, 2-equivalent magenta couplers of the formula I used according to the invention are listed below:

Further 2-equivalent magenta couplers of the formula I which are described in US Pat used the short-term processing process according to the invention can be in DE-A 36 22 007, 23 24 103 and 36 25 616.

An alkyl radical represented by R⁴ or R⁵ in formula II contains 2-10 C atoms and may be straight-chain or branched. An alkyl radical represented by R⁶ contains 1-19 C atoms and may be straight-chain or branched. An alkylene group represented by R⁷ contains up to 12 C atoms; an arylene group is, for example, o-, m- or p-phenylene. A ring completed by R⁴ and R⁵ is a cyclic amino group, e.g. As morpholino, piperidino or pyrrolino. A ring completed by R⁴ and R⁶ is the residue of a cyclic amide, examples of compounds of formula II are listed below:

Under a short-term processing process, one is opposed The conventional development process greatly shortened Processing process understood, mainly the duration of the development will be greatly shortened can.

While the development time in the conventional method at temperatures between 25 and 45 ° C for 3 minutes and more, the present invention relates to a process in which the development in the specified Temperature range within 10 seconds to 3 minutes at the most. It is preferred needed for development less than 1 minute.  

In addition to the development of the invention Short-term processing usually a treatment step for removing the formed silver and the remaining silver halide, both also can be done in separate treatment steps. Conveniently, These are also these additional treatment steps strong compared to the conventional method shortened.

The processed by the process according to the invention color photographic recording material contains at least a photosensitive silver halide emulsion layer and preferably a sequence of several such photosensitive silver halide emulsion layers and optionally non-photosensitive therebetween Binder layers, wherein according to the present invention at least one of the existing photosensitive Silver halide emulsion layers a 2-equivalent magenta coupler of formula I, emulsified with an oil former the formula II, is assigned.

The oil former used in the process according to the invention Can be used alone or together with other well-known oil producers however, if the magenta coupler dissolved in a mixture of oil formers such mixture preferably to more than 50 wt .-% of an oil former of the present invention.

The photosensitive layers used in the photosensitive layers Silver halide emulsions can be used as halide  Chloride, bromide and iodide or mixtures thereof. They are preferably high-chloride emulsions with a bromide content of less than 1 mole%. There Materials with such silver halide emulsions for the Short-term processing are particularly well suited, The present invention also relates to a color photographic Recording material with at least one photosensitive silver halide emulsion layer, their silver halide consists of more than 99% silver chloride and a 2-equivalent pyrazolone type coupler and an oil former are assigned, wherein the 2-equivalent magenta coupler of general formula I corresponds and the oil former corresponds to the general formula II.

The emulsions may be heterodisperse, or also be monodisperse emulsions, which are preferred have an average particle size of 0.3 microns to 1.2 microns. The silver halide grains may also be a layered one Have grain structure.

The emulsions can be chemically and in the usual way or spectrally sensitized; You can also go through be stabilized suitable additives. Suitable chemical Sensitizers, spectral sensitizing dyes and stabilizers are, for example, in Research Disclosure 17 643 (December, 1978); is referenced in particular to Chapters III, IV and VI.

The color photographic recording material according to the invention preferably contains at least one silver halide emulsion layer each  for the recording of light each of the three spectral regions red, green and blue, which are known in the art By suitable sensitizing dyes spectrally sensitized.

Between layers of different spectral sensitivity is usually a non-photosensitive intermediate layer arranged, the means for stopping the Incorrect diffusion of developer oxidation products included can. If more silver halide emulsion layers same spectral sensitivity are present, can they may be immediately adjacent to each other or so arranged be that between them a light-sensitive Layer with different spectral sensitivity is located (DE-A 19 58 709, DE-A 25 30 645, DE-A 26 22 922).

Inventive color photographic recording materials usually contain in spatial and spectral Assignment to the silver halide emulsion layers different Spectral sensitivity Color coupler for Generation of different partial color images Cyan, Purple and yellow, with the present with the oil former Invention dispersed pyrazolone magenta in the general green-sensitive silver halide emulsion layer assigned.

Under spatial allocation is to be understood that the Color couplers are in such a spatial relationship with the silver halide emulsion layer is that a  Interaction between them is possible, which is a pictorial Agreement between in the development formed silver image and that produced from the color coupler Color image allows. This is usually achieved by in that the color coupler in the silver halide emulsion layer itself is included or in one for this adjacent optionally non-photosensitive binder layer.

By spectral assignment is meant that the spectral response each of the photosensitive silver halide emulsion layers and the color of each one spatially assigned color coupler generated partial color image in a certain relationship to each other each of the spectral sensitivities (red, Green, blue) a different color of the relevant sub-color end image (in general, for example, the colors cyan, purple or yellow is assigned in this order.

Thus, in preferred embodiments, red-sensitive silver halide emulsion layers have associated therewith at least one non-diffusing color coupler for forming the cyan partial color image, typically a phenol or α- naphthol type coupler. Green-sensitive silver halide emulsion layers is associated with at least one non-diffusing color coupler for generating the purple partial color image, wherein optionally in addition to the 2-equivalent magenta coupler used in the invention also other magenta z. B. of the type of indazolone or pyrazoloazole find use.

Blue-sensitive silver halide emulsion layers Finally, there is at least one non-diffusive color coupler assigned to generate the yellow partial color image, usually a color coupler with an open-chain Ketomethylene group. Color coupler of this type are known in large numbers and in a variety of patents described. Exemplary here on the Publications "Farbkuppler" by W. PELZ in "Mitteilungen from the research laboratories of Agfa, Leverkusen / Munich ", Volume III, page 111 (1961) and K. VENKATARAMAN in "The Chemistry of Synthetic Dyes", Vol. 4, 341-387, Academic Press (1971).

For the recording materials used in the invention are the usual supports, z. B carrier from cellulose esters, e.g. As cellulose acetate and polyesters. Also suitable are paper supports, if appropriate may be coated z. With polyolefins, especially with polyethylene or polypropylene. directed is referred to Research Disclosure 17 643, Chapter XVII.

As a protective colloid or binder for the layers of Recording material are the usual hydrophilic film-forming Means suitable, for. As proteins, especially gelatin. Gelling aids and plasticizers may be used become. Reference is made to Research Disclosure 17 643, Chapter IX, XI and XII.

The layers of photographic material can be found in the  hardened in the usual way, for example with hardeners, the at least two reactive oxirane, aziridine or acryloyl groups contain. Furthermore, it is also possible to Layers according to the method described in DE-A 22 18 009 to harden. It is also possible the photographic Layers or the color photographic multilayer materials with hardeners of diazine, triazine or 1,2- To cure dihydroquinoline series or with hardeners from Vinyl sulfone type. Other suitable curing agents are off DE-A 24 39 551, DE-A 22 25 230, DE-A 24 39 551 as well from Research Disclosure 17 643, Chapter X. Especially pronounced is the stabilizing effect of the invention Oil former when activating carboxyl groups Hardening agent, e.g. B. carbamoylpyridinium or Carbamoyl oxypyridinium salts are used.

Further suitable additives are in the Research Disclosure 17 643 and in the "Product Licensing Index" of December 1971, pages 107-110.

Suitable color developing agents for the material according to the invention are in particular those of the p-phenylenediamine type, for. 4-amino-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N- β- (methanesulfonamido) ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl N- β- hydroxyethylaniline sulfate, 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N- β- hydroxyethyl-p-phenylenediamine. Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73, 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, pp. 545 et seq.

After color development, the material is usually bleached and fixed. Bleaching and fixation may be carried out separately or together. As bleaching agent, the usual compounds can be used, for. B. Fe ³⁺ salts and Fe ³⁺ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc. Particularly preferred are iron-III complexes of aminopolycarboxylic acids, in particular z. As ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic, Alkyliminodicarbonsäuren and of corresponding phosphonic acids. Suitable bleaching agents are persulfates.

Example 1

10 g of a purple coupler are in 10 ml of oil and Dissolved 30 ml of ethyl acetate. This solution is at 55 ° C with a high-speed mixer in 200 g of 7.5% aqueous Gelatin with 1.5 g of sodium dodecylbenzenesulfonate as Wetting agent dispersed. Then it gets low boiling solvent removed in vacuo.

The dispersions were microscopic to crystalline Particles and their particle size immediately after production and after 7 days refrigerated storage examined. there showed in all cases that the dispersants stable are, d. H. do not crystallize, and differently in any case, but for photographic purposes have useful size distributions.

The resulting dispersants were mixed with 190 ml of a Silver chloride emulsion containing 6.4 g of silver and ca. 12 g of gelatin, mixed and in the usual way on polyethylene shed coated base.

From the layers thus obtained, the color formation kinetics curves were determined by measuring the increase in color density A over time with an aqueous dilute solution of 3-methyl-4-amino-N-ethyl-N- β -methanesulfonamidoethylaniline having a pH of 10 was measured. The evaluation was carried out by graphical determination of the initial increase

and by determining the time T necessary for the color density

to achieve. The results are recorded in Table 1.

Reference compounds

Table 1

Characteristic is also the course of the colorization curves; It can be seen that the graphs of the 2-equivalent couplers in the oil formers of the invention are similar to those of the 4-equivalent couplers in virtually all oil paintings. The recorded curves of the 2-equivalent couplers in the oil former not according to the invention show an S-shaped course with a partly large gradient in the medium density range, but at a later point in time during development, corresponding to a greater time T.

The curves clearly show what the photographic one is Development is observed, namely the advantageous properties of the common application of 2-equivalent couplers with the oil formers according to the invention.

example 2

The samples obtained in Example 1 were exposed and developed:

Development 1 a) Color developer - 3.5 min - 33 ° C benzyl alcohol 15 ml ethylene glycol 15 ml Hydroxylamine 3 g 3-Methyl-4-amino-N-ethyl-N- ( β- methanesulfonamidoethyl) aniline sulfate 4.5 g K₂CO₃ 32 g K₂SO₃ 2 g KBr 0.6 g Disodium salt of 1-hydroxyethane-1,1-diphosphonic acid 1 g make up to 1000 ml with water; pH 10.2. @ b) Bleach-fix bath - 1.5 min @ Ammonia solution (28%) 35 ml EDTA 30 g Na₂SO₃ 15 g ammonium 100 g Sodium (EDTA) iron-III-complex 60 g make up to 1000 ml with water; pH 7. @ c) watering - 3 min

Development 2 a) Color developer - 45 s - 35 ° C triethanolamine 9.0 g NN-diethyl 6.0 g diethylene glycol 0.05 g 3-methyl-4-amino-N-ethyl-N-methanesulfonamidoethyl-aniline sulfate 6.0 g potassium 0.2 g triethylene 0.05 g potassium carbonate 22 g potassium hydroxide 0.4 g Ethylenediaminetetraacetic acid di-Na salt 2.2 g make up to 1000 ml with water; pH 9.2. @ b) Bleach-fix bath - 45 s - 33 ° C @ ammonium 75 g sodium bisulfite 13.5 g ammonium acetate 2.0 g Ethylenediaminetetraacetic acid (ferric ammonium salt) 57 g Ammonia 25% 9.5 g acetic acid 9.0 g c) watering - 2 min - 33 ° C

Table 2

Development Results: Development 2 (Development 1)

The samples were re-measured after 6 and 15 days, respectively. there could in case of being processed after development 1 Samples no sensitometic change can be detected. Table 2 shows:

• 1. Long-term development processes yield both for 2-equivalent and 4-equivalent magenta couplers no sensitometric changes during storage of the developed photographic material.
• 2. Photo material developed in short-term processes then shows no sensitometric change in storage, when 4-equivalent magenta couplers are used become.
• 3. Sensitometric change on storage is observed when 2-equivalent pyrazolone coupler is used reach; it can be suppressed, though the oil former of the invention, with 4-equivalent couplers in short-term processing or with 2-equivalent couplers in long-term processing no noticeable accelerating effect show, get used.

The effects mentioned in this example are underlined by the following observations with the same materials:
Change of development conditions by

• a) development at low developer pH,  
• b) shortening the development time,
• c) Use of slower developing (bromide-containing) Silver.

All 3 variations have the same effect, namely an increase in the difference of the sensitometric Data after storage on the one hand and immediately after processing, on the other hand.

For faster development, z. B. by drastic Change in the layer pH higher values (alkaline) Achieve this rate of change Storage reduced.

example 3

A substrate made of polyethylene coated on both sides Paper was provided with the following layers. The quantities refer to 1 m²:

• 1. A substrate layer of 200 mg gelatin with KNO₃- and chrome alum additive,
• 2. a blue-sensitive silver chloride emulsion layer from 600 mg of AgNO₃ with 2100 mg of gelatin, 1.1 mmol Yellow coupler, 27.7 mg of 2,5-dioctylhydroquinone and 1200 mg of tricresyl phosphate,  
• 3. An intermediate layer of 1300 mg gelatin, 80 mg 2,5-dioctylhydroquinone and 100 mg of tricresylphosphate,
• 4. A green-sensitive silver chloride emulsion layer of 530 mg of AgNO₃ with 750 mg of gelatin, 0.625 mmol magenta couplers as shown in the following Table 3, 118 mg of α - (3-t-butyl-4-hydroxyphenoxy-myristinsäureethylester, 43 mg of 2,5-dioctylhydroquinone and Oil formers, as shown in Table 3 below,
• 5. An intermediate layer of 1550 mg gelatin, 285 mg UV absorber Tinuvin 343®, 80 mg dioctylhydroquinone and 650 mg of tricresyl phosphate,
• 6. A red-sensitive silver chloride emulsion layer from 400 mg of AgNO₃ with 1470 mg of gelatin, 0.780 mmol Cyan coupler, 285 mg dibutyl phthalate and 122 mg tricresyl
• 7. A protective layer of 1200 mg gelatin and 134 mg Tinuvin 343®,
• 8. A hardening layer of 400 mg gelatin and 400 mg an instant hardener (CAS Reg No. 65 411-60-1).

In layers 2 and 6 the following couplers were used:
yellow coupler

Cyan coupler

The coupler and silver halide levels in layer 4 apply in the event that the magenta coupler is a 4-equivalent coupler is. When using a 2-equivalent magenta coupler is, its order quantity is 0.5 mmol and the corresponding amount of silver chloride corresponds to 420 mg AgNO.

Various recording materials were produced, which differed only in the layer 4, as from Table 3 below:  

Table 3

The materials were exposed with a gray wedge and according to both development processes described in Example 2 (Development 1 and Development 2).

Long-term processing proves all materials neutrally balanced across the entire density range, d. H. there was no color transition in the transition to higher Densities to watch.  

The short term processing showed after processing another result; proved in the very low densities the samples are also neutral gray. With but increasing density tipped the materials 3, 4 and 5 and were then in the range of maximum color density strong green. Only after several days of storage at room temperature or 2 hours of storage at 65 ° C were also these materials are neutral in color.

The remaining materials, d. H. the materials 1 and 2 (4-equivalent coupler) and materials 6 to 10 (2-equivalent coupler) with the low silver and Coupler application was found to be neutral after processing Gray.

Claims (5)

A process for producing colored images comprising subjecting an imagewise exposed color photographic recording material to at least one photosensitive silver halide emulsion layer having a pyrazolone type 2-equivalent magenta coupler and an oil former to a short-term processing process, characterized in that the 2-equivalent magenta coupler is the following general Formula I corresponds in which mean
n 1 to 5;
m 1 to 3;
X is a leaving group of the formula -S-R³;
R¹ is halogen, alkoxy, alkylthio, acylamino, sulfamoyl or alkoxycarbonyl;
R 2 is halogen, cyano, thiocyanato, alkoxy, alkyl, acylamino, alkoxycarbonyl;
R 3 is alkyl, aryl or a heterocyclic group;
and that an amide compound of the general formula II is used as the oil former in which mean
R⁴ alkyl;
R⁵ alkyl; or R⁴ and R⁵ together or R⁴ and R⁶ together form the radical to complete a 5- or 6-membered heterocyclic ring;
R⁷ is alkylene or arylene;
p 0 or 1. 2. The method of claim 1, wherein the short-term processing process a development treatment step  and one or more treatment steps to remove the formed silver and the remainder Silver halide and wherein the development treatment step at temperatures between 25 and 45 ° C takes less than 3 minutes. 3. The method according to claim 2, characterized that the development treatment step at temperatures between 25 and 45 ° C less than 1 minute lasts. 4. The method according to claim 1, characterized that diethylauramide is used as an oil former. 5. A color photographic recording medium comprising at least one light-sensitive silver halide emulsion layer whose silver halide is more than 99 mol% silver chloride and which has a 2-equivalent pyrazolone type coupler and an oil former, characterized in that the 2-equivalent magenta coupler is represented by the following general formula I. in which mean
n 1 to 5;
m 1 to 3;
X is a leaving group of the formula -S-R³;
R¹ is halogen, alkoxy, alkylthio, acylamino, sulfamoyl or alkoxycarbonyl;
R 2 is halogen, cyano, thiocyanato, alkoxy, alkyl, acylamino, alkoxycarbonyl;
R 3 is alkyl, aryl or a heterocyclic group;
and that as the oil former is an amide compound of general formula II in which mean
R⁴ alkyl;
R⁵ alkyl; or R⁴ and R⁵ together or R⁴ and R⁶ together form the radical to complete a 5- or 6-membered heterocyclic ring;
R⁷ is alkylene or arylene;
p 0 or 1.