DE1926877A1 - Process for the production of multicolor photographic images - Google Patents

Description

Eastman Kodak Company, 343 State Street, Rochester, New York State, United States of America

Process for the production of multicolor photographic

Images

The invention relates to a method for producing multicolored photographic images, in particular using automatic high-speed developing devices operated at higher temperatures, according to which a photographic recording material intended for color photography, consisting of a support, superposed silver halide emulsion layers and optionally intermediate and / or top layers, is exposed imagewise whereupon in the emulsion layers of the exposed recording material, optionally after prior hardening of the layers, wammim *. Color images are developed and any undeveloped silver halide and any silver images that may be present are removed.

The production of multicolored photographic images takes place as is known by exposure and development of multilayer photographic recording materials which are disclosed in As a rule, at least three differently sensitized SiI overhalide emulsion layers of which one opposite

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via light of the red region of the spectrum j the second opposite Light of the green part of the spectrum and the third sensitive to light of the blue part of the spectrum is. The blue-sensitive emulsion layer can be the outermost layer of the three superposed on a support form light-sensitive layers and from the green- and red-sensitive emulsion layer through a yellow filter layer be separated. Is it such for color photography certain photographic recording materials are recording materials containing color couplers Emulsion layers or these layers arranged adjacent to them incorporated dye formers or coupler compounds. Such coupler-containing photographic recording materials After exposure, developer solutions containing color developing agents of the p-phenylenediamine type are used color developed. The development of the exposed recording materials can either by the so-called negative process, in which by immediate development with the help of color developers Color negatives are generated, or according to the so-called reversal process, first with the help of black and white developers and then with the help of color developers a color positive is generated. The production of such multilayer recording materials intended for color photography is z. As described in U.S. Patents 2,322,027 and 2,252,718.

In the development of such exposed recording materials The emulsion layers which are wetted with the developer solutions and usually contain gelatin swell and become comparatively soft, so that they are often disadvantageously abraded and deformed. It has therefore proven to be useful proved to cure the emulsion layers applied to the substrate as much as possible. It was found however, that such hardening is usually not sufficient,

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the abrasion that often occurs during development and to prevent other damage to the emulsion layers, especially when development is carried out using automatic development devices. There are therefore Processes have already become known according to which the exposed photographic recording material is shortly before development with a solution containing a hardening agent, e.g. B. an aldehyde-containing, for example formaldehyde-containing solution, is pretreated. The known ones containing hardeners However, solutions have numerous disadvantages. So have z. B. formaldehyde solutions for hardening gelatine-containing Emulsion layers proven to be useful, but have the disadvantage that the formaldehyde in high concentrations, z. B. in concentrations of about 55 g per liter of solution, must be used to sufficiently harden the gelatin to effect. Hardener solutions have therefore already been used which contain other hardeners in addition to formaldehyde contain. So z. B. in US Pat. No. 3,220,849 describes a hardener solution which, in addition to Formaldehyde contains succindialdehyde. Furthermore, in the French Patent specification 1 543 060 describes a hardener solution which, in addition to formaldehyde, bis-bisulfite adduction products a dialdehyde, e.g. B. of succindialdehyde, glutaraldehyde or their derivatives. Also known are hardening agent solutions whose hardening agents are made from aluminum salts consists. The known hardener solutions, however, have the disadvantage that they do not sufficiently harden the Emulsion layers effect when the exposed photographic Recording materials at elevated temperatures and / or using automatic developing devices are developed, since under the specified conditions the recording materials are subjected to comparatively high stresses are exposed.

It is already known to shorten the development time

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Development at elevated temperatures, e.g. B. at temperatures of about 38 to 52 ⁰ C to perform. At such temperatures, however, the hydrophilic emulsion layers, in particular gelatin-containing emulsion layers, of the photographic recording materials to be developed soften and swell very strongly, so that they are very easily damaged, e.g. B. abraded or deformed, can be. Such damage usually occurs when the exposed recording materials containing the swollen emulsion layers are transported from one treatment solution to the other during development and fixation, whether by hand or with the aid of racks or hanging devices, but especially when using continuous ones Development devices, ζ. B. of those in which the photographic recording material to be developed is guided through the various processing solutions with the aid of a roller transport system and is brought into contact with the transport rollers and other components of the automatic developing device.

The problem of multi-layer, e.g. B. intended for color photography photographic recording materials at elevated temperatures, in particular using roller transport systems having continuously operating developing devices without damage to develop, fix and drying has not yet been solved satisfactorily. For example, such recording materials hardened after exposure in the usual known manner with the aid of hardener solutions, e.g. aldehyde solutions, in this way the damage that usually occurs during development can be reduced, but not completely turned off. It has been shown that even the hardened recording materials in the development in Automatic high-speed developing devices often suffer damage because of the edges and surfaces of the emulsion layers repeatedly with transport rollers and other machine parts, e.g.

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Guiding and guiding devices come into contact, so that parts of the swollen emulsion ^{layers are often detached from the substrate and deposited on the film surface in the form of "impurities 11.} Damage of this kind occurs particularly when the recording material to be developed is affected are sheet films intended for color photography, since their edges hit the transport rollers and guide rails of the developing device particularly frequently, so that the emulsion layers are "split off", that is, small pieces of the emulsion layer break off at the corners and cards of the film sheet The elevated temperatures prevailing in the developing devices often also cause other damage, for example the swollen emulsion layers can adversely stick to the transport rollers or the sheets passing through the drying chamber Films can stick together. The damage to the developed films, presumably due to the contact of the emulsion layers with the transport rollers running through the drying chamber, is sometimes expressed in the appearance of so-called "orange peel" film surfaces (orange peel-like textures on the film surface).

The object of the invention is to provide a method which can be carried out quickly and easily, according to which the exposed multilayer recording material can be developed and fixed advantageously even at higher temperatures, in particular using continuously operating automatic high-speed developing devices, in order to produce high quality multicolored photographic images can. ■ -. -

The invention is based on the surprising finding that the specified object is thereby achieved in a particularly advantageous manner is solvable that the exposed recording material in exactly

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hardened in a defined manner, d. h, is pre-cured before development and post-cured after development.

The invention relates to a process for producing multicolored photographic images, in particular using them automatic tendon developing machines operated at higher temperatures, after which one for color photography certain photographic recording material, consisting of a layer support, arranged one above the other Silver halide emulsion layers, and optionally intermediate and / or top layers, is exposed imagewise, whereupon in the emulsion layers of the exposed recording material, ge-P if necessary after previous hardening of the layers, flMtai Developed color images and removed 4MHBlI undeveloped silver halide and any silver images that may be present which is characterized in that the silver halide emulsion layers of the exposed recording material is pre-cured with the aid of a solution containing aldehyde hardener before development and after development with the aid post-cures with an acidic zirconium salt solution »

After the practice of the invention, the development and further processing of the exposed photographic recording material therefore advantageously even at elevated temperatures. temperatures of z. B. about 38 to 52 ° C and / or using ™ of development devices having transport racks or transport rollers be carried out because of the pre-hardening effected with the aid of aldehyde hardening agent solutions the swelling of the emulsion layers and reduced by the post-hardening brought about by means of zirconium salt solutions Resistance of the emulsion layers is increased even further.

If the method of the invention is used as part of a so-called color negative process carried out, it has been found to be particularly advantageous to post-cure immediately after color development to undertake. Contains the acid used for this

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Zirconium salt solution also a silver halide solvent, so it works as a hardening-stop-fixing solution, * such as B. is illustrated in Example 1 given below.

If the method of the invention is used in the context of a so-called color reversal method carried out, the one used for post-curing either before or after reversal color development acidic zirconium saline solution either without adding more Additions as a hardening stop solution or with the addition of a Silver halide solvent at the same time as a fixing solution can be used as illustrated in Example 3 given below.

To carry out the method of the invention can, as already mentioned, multilayer recording materials intended for color photography are advantageously used which are in the form of roll films or sheet films. Are the photographic recording materials in shape of sheet films, which after exposure at elevated temperatures, z. B. developed in roller transport systems having, continuously operating development devices should be, so it has proven to be useful for Post-hardening is carried out with an acidic zirconium salt solution, which also contains an aluminum salt hardening agent, to be used, in particular, to prevent the occurrence of "splitting off" of the emulsion layers. It has also shown that to carry out the after development post-curing of the exposed recording material, the zirconium salt present in the curing agent solution neither by an aldehyde curing agent nor by a Aluminum hardening agent is replaceable. In order to carry out of the method of the invention required gradual hardening of the recording material to be developed to effect, a post-hardening solution must be used that contains a zirconium salt or in addition to a zirconium

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salt also contains an aluminum salt. Surprisingly The combination of zirconium and aluminum salts has proven to be particularly advantageous because it allows post-hardening Recording materials versus those in automatic developing machines The prevailing elevated temperatures are so resistant * that exposed color films or papers complete in the manner indicated within about 10 minutes can be developed and dried, whereas, according to the known methods, devolution and drying times up to 2 hours are required.

^ The method of the invention can be carried out using coloring films or papers which, after exposure, are transported from one treatment solution to the other with the aid of racks or suspension devices, with damage to the emulsion layers being reduced or prevented by the specified pre- and post-curing will. However, it has been found particularly advantageous to carry out the process of the invention using automatic developing devices, e.g. B. of the type shown in the accompanying drawing, since in this way the exposed recording materials intended for color photography are developed in a very short time and in a particularly advantageous manner and ^{damage to the emulsion layers caused by "splitting 1} " or sticking together is reduced or prevented The automatic developing devices used can be designed differently depending on the type and shape of the exposed recording material to be developed. An automatic developing device as shown in the accompanying drawing in the Snema has proven to be very suitable.

The automatic developing device shown in the drawing consists of several containers arranged next to each other, which contain the individual development phases.

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speaking treatment solutions, as well as a drying chamber * The recording materials to be developed in the form of color film strips or sheets are transferred through the tanks filled with the treatment solution and the drying chamber Continuously guided with the help of a roller transport system. Of the individual sections of the developing device, in the drawing are the aldehyde pre-hardening section I, the color developing section II, the zirconium salt post-hardening section III and the drying section IV are shown in the diagram. the exposed photographic recording materials, e.g. B. Paint films F are fed to the aldehyde precure section and then by the transport rollers, which are offset from one another, through the individual sections of the developing device directed. A continuous developing device of this type is described, for example, in US Pat 3 025 779 described in detail.

In the commonly used developing device shown in the drawing, the guide rollers are arranged at the top and bottom of the tanks so that the recording material to be developed travels a sinusoidal path through the tanks. For the continuous development of an exposed cinema color film, it has proven to be useful to provide a series of spools or detached guide rollers in the tanks so that the recording material to be developed is guided helically around the specified spools or rollers and in the usual known manner through the individual treatment solutions and is finally transported into the drying section without the treated recording material, e.g. B. to be developed and to be dried'Blattfilm is damaged in the specified manner in that z. B. in the tanks containing the treatment solutions, the emulsion layers of the film are lifted or split off or in the drying chamber the film surface ^{forms a so-called "orange peel surface 11} " on contact with the rollers or when

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Contact with another film stuck to this one.

To carry out the process of the invention, the exposed material is precured and reduced in swelling capacity For photographic recording material, an acidic aldehyde hardener solution is preferably used as hardening agent has, as already mentioned, only one aldehyde hardener, especially formaldehyde, proved to be suitable. When formaldehyde is used as a hardening agent, it has been found to be proven to be useful in a concentration of about 100 Use up to 200 ml 37 liter formaldehyde per liter of solution.

If formaldehyde is used together with a dialdehyde, so it has proven to be useful, approximately per liter of solution Use 0.5 to 10 g of dialdehyde and about 5 to 15 g of formaldehyde.

To carry out the method of the invention, an aldehyde hardening agent solution has proven to be particularly advantageous, that from an aqueous solution, having a pH of about 2 to 7, of a mixture of formaldehyde Bis-bisulfite addition product of a dialdehyde, whose Dialdehyde component carries two aldehyde groups, which are linked by a linear hydrocarbon chain with 2 to 3 carbon atoms, by no more than 3 alkyl and / or alkoxy radicals with 1 to 4 carbon atoms are substituted, are separated from each other. Typical suitable such dialdehyde bisulfite addition products are z. B. the bis-bisulfite addition products of ß-methylglutaraldehyde, glutaraldehyde, a-methylglutardi «* aldehyde, maleindialdehyde, succindialdehyde, cyclopentanedicarboxaldehyde, Methoxysuccinaldehyde, α, α-dimethylglutaraldehyde, Λ, β-dimethylglutaraldehyde, Methyl succinic dialdehyde, a-methyl-ß-ethoxyglutaraldehyde, α-butoxyglutaraldehyde, s-isopropoxysuccindialdehyde and butyl maleic dialdehyde.

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The bis-bisilfit addition product has proven to be particularly suitable of succindialdehyde "

Dialdehydes of the following general ones have also been found to be suitable Formula proven;

OHC— (CHR ₁ ) ~ X- (CHR ₁ ) -

CHO

in which:

R- is a hydrogen atom or a short-chain one Alkyl radical, where the substituents R- are the same or different from one another Can have meaning;

X is an oxygen, sulfur or selenium atom

or a nitrogen group of the formula = NR ₂ , in which R _{2 is} a hydrogen atom or a short-chain alkyl radical and

η = 1 or 2.

Typical suitable dialdehydes of this type are ζ. Β ,;

Thio-bis-acetaldehyde OHC-CH ₂ -S-CH ₂ -CHO

N-methylamino-bis-acetaldehyde ÖHC-CH ^ -N-CH ^ -CHO

2 ι Ζ

Hydrochloride £ _H (

Imino-bis-acetaldehyde OHc-CH ₂ -NH-CH ₂ -CHO

9 η 9 8 8 7/13 9 3

Oxy-bis-acetaldehyde OHC-CH ₂ -O-CH ₂ -CHO

Seleno-bis-acetaldehyde OHC-CH ₂ -Se-CH ₂ -CHO

Used to pre-harden the exposed recording materials Aldehyde hardener solutions used that contain formaldehyde bisulfite addition products of the specified dialdehydes » So it has proven to be useful to use the formaldehyde in concentrations of about 2 to 56 g / l solution and the dialdehyde bisulfite addition product to be used in concentrations of about 1 to 100 g / l solution. The optimal concentration eri

ψ of formaldehyde and dialdehyde bisulfite addition product depend on various factors, e.g. B. on the desired degree of hardening of the photographic color recording material to be hardened, the hardening activity of the dialdehyde bisulfite addition product used and the like »The specified concentration ranges have proven to be particularly advantageous when the photographic recording materials to be hardened are color films with gelatin-containing emulsion layers. Aldehyde hardener solutions of the specified composition can also be used to pre-harden photographic recording materials with hydrophilic colloid emulsion layers other than gelatin emulsion layers, but in this case they are generally less effective.

w sam. It has proven to be useful to add the dialdehyde bisbisulfite addition products to the aldehyde hardener solutions in the form of alkali metal salts or salts of nitrogen bases, ζ. B. of ammonium or amine salts, to be incorporated *

Those used to carry out the method of the invention Aldehyde hardener solutions that contain a mixture of formaldehyde and dialdehyde bisulfite addition product have the Advantage that they smell far less unpleasant than solutions, the dialdehyde only, e.g. B. succindialdehyde, or a

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Dialdehyde precursor compound, ζ. B. 2,5-dimethoxytetrahydrofuran, contain. They also have the advantage that with their help the degree of hardening and swelling of the treated emulsion layers can be controlled in an advantageous manner »Finally, they also have the advantage that for their production comparatively little formaldehyde compared to that used for production of hardening agent solutions containing only formaldehyde as hardening agent, is required »

The precuring of the exposed photographic recording materials is usually controlled in such a way that the emulsion layers when using a color negative process so strong at the end of color development, or if a color reversal process is used, at the end of black and white development are swollen that their thickness by about 100 to 3001, based to the layer thickness in the dry state, increases.

The following has been used to determine the percentage swelling A device known as a "swelling meter" has been found to be useful, which continuously measures the amount of water in the emulsion layers gelatin present in photographic recording materials, as it is e.g. B. in "Photographic Science and Engineering ", Volume 8, page 275 (1964) will.

Particularly suitable for carrying dts method of the invention, magnesium sulfate j formaldehyde and Aldehydhärtungslösungen containing Aldehydbisulfitverbindungen _s are as inter alia used in an advantageous manner in the examples below, are for. B. described in French patent 1,544,954. It has been shown that the use of magnesium sulfate, optionally in combination with other salts, such as sodium sulfate, has the advantage of not crystallizing out of the solution as easily as other salts,

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so that the rollers and walls of the containing such solutions Tanks of automatic developing devices are not disadvantageous Way to be contaminated by crystal deposits.

The acidic zirconium salt solution used to post-cure the developed photographic recording materials, which may also contain an aluminum salt, is essential for the successful implementation of the process of the invention. So she is z. B, not by an acidic aluminum saline solution, e.g. B. a commonly known "Hyposluminiumfixierlosuisg ^ j. It can also not be used for pre-hardening the exposed recording material * It evidently causes a reaction of the zirconium and possibly aluminum salts contained therein with the pre-hardened and developed with the help of aldehydes Emulsion layers with the formation of particularly resistant emulsion layers, which are resistant to the abrasion caused by the roller and guide devices of the developing apparatus, so that neither roller marks remain on the fila surfaces, nor a detachment of the emulsion, titan th from the support or the film surfaces sticking together » z »B _{e occurs} when passing through the hot drying chamber.

The post-curing solutions used to carry out the process of the invention can contain a wide variety of water-soluble zirconium salts, especially when it is a question of post-curing emulsion layers "^" whose binding agent consists largely of gelatin. B. Zirkoniiaaswlfat wid zirconium nitrate »also complex salts, z. B ₈ zirconium sulphate, whose formula is probably H ₂ ZsO (SO ₄ ) ₂ * 3H ^ O, as well as zirconium sulphate, zirconium sodium sulphate and the like. Zirconyl sulphate has proven to be particularly advantageous.

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The one used to post-cure the developed emulsion layers acidic zirconium salt solution can additionally contain a wide variety of water-soluble aluminum salts, in particular when it comes to post-curing emulsion layers, whose binding agent consists mainly of gelatin. Typical suitable aluminum salts are e.g. B. Aluminiuincfelorid, aluminum nitrate, Potassium aluminum sulfate and the like. Aluminum sulfate has proven to be particularly advantageous.

As already mentioned, the acidic zirconium salt solutions are used in a particularly advantageous manner after the color development of the exposed recording materials intended for color photography. If post-curing takes place at 38 ° C., zirconium salt solutions have proven to be expedient, which contain about 2 to 10 g of zirconium salt, e.g. B, zirconyl sulfate. Any additional aluminum salts present, for example aluminum chloride, are expediently in concentrations of QtMa. 5 to 15g per liter of solution if post-curing takes place at 38 ° C. The salt concentrations used depend on the desired degree of hardening of the emulsion layers, which in turn is influenced by various factors, e.g. the temperature used and the type of used , optionally a developing device having a roller transport system. A post-curing solution has proven to be useful which contains about 2 g of zirconyl sulfate and about 9 g of aluminum sulfate per liter of solution. It has been found to be useful to adjust the pH with a strong acid, e.g. B. sulfuric acid, set to about 3 to 6. A pH value of 4.0 has proven to be very advantageous. Optionally, the acidic zirconium salt solution can be buffered in a conventional manner, e.g. Is as illustrated by the addition of sodium acetate / acetic _e as in the examples below "in which the zirconium salt solution optionally added thiosulfate may around

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-10-

a commonly known thiosulfate compound, ζ. B. to alkali metal or ammonium thiosulfate.

To carry out the method of the invention it turns out the aldehyde hardeners used for the pre-hardening of the exposed recording materials are often expedient to neutralize after the pre-hardening, especially if the aldehyde compounds used are the following Adversely affect color development of the emulsion layers. This is e.g. B. the case when using color couplers, that react with formaldehyde. To prevent the conversion of such color couplers into the color developer solution Formaldehyde, the formaldehyde used for pre-hardening, is expediently before the color development is carried out neutralized. Typical suitable aldehyde neutralization compounds are e.g. B. hydroxylamine, for example in the form of Hydroxylamine sulfate, also carbohydrazide, semicarbazide, hydrazine, j & abb & hydrate, biuret, aminoguanidine, methyl semicarbazide and the water-soluble salts of the specified compounds. Suitable such aldehyde neutralizing compounds are e.g. in columns 4 and 5 of U.S. Patent 3,168-400.

The advantageously usable components of the suitable for carrying out the method of the invention, for the Color photography of certain recording materials, including the appropriate cyan, magenta and yellow couplers, are z. See, for example, U.S. Patent 3,141,771 in detail described. Process for the production of such photographic images Recording materials are z. B. in the United States patents 2,322,027 and 2,252,718. The coupler-free recording materials known from US Pat. No. 2,252,718 are expediently after color reversal process with the help of coupler-containing developer solutions, as z. B. in the specified USA patent 2 252 718, developed, it being particularly advantageous

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sen, according to that described in Example 3 given below Process the developed recording material first with the help of a ferricyanide-containing bleaching solution bleaching and then fixing with the aid of an acidic zirconium salt solution containing a fixing agent. as The process described in Example 2 of US Pat. No. 3,141,771 for the reversal development of exposed images has proven to be useful photographic recording materials, the developed following the final color development Recording material advantageously according to the process of the invention with an acidic zirconium saline solution is post-cured.

The following examples are intended to explain the invention in more detail. In the examples, the following, with “precuring solution I to III "designated aldehyde hardener solutions are used;

Pre-hardening solution I

Sodium sulfate 150.0 g

Formaldehyde 10.0 g

Glacial acetic acid 1.7 ml

Sodium bromide 2.0 g

Succindialdehyde 1.0 g

filled with passer to 1.0 liter

with sodium hydroxide the -

pH adjusted to about 4-7.

Pre-hardening solution II

Succindialdehyde 10.0 g

Sodium acetate 10.0 g

made up to 1.0 liter with water

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Pre-hardening solution III

Succindialdehyde bis-bisulfite 11.42 g

Sodium sulfate, anhydrous 85.72 g

Sodium Acetate, Anhydrous 25.14 g

Sodium diacetate 0.29 g

Magnesium sulfate heptahydrate 240.00 g

Formalin, 37lig 33.33g

Filled up with water to 1.0 liter, pH adjusted to 6.3

example 1

Implementation of the process with the help of color negative development

To produce a photographic material intended for color photography, a Support made of cellulose acetate or linear polyester film Gelatin-silver halide emulsion layers which are arranged one above the other and are sensitive to red, green or blue light applied, with a yellow filter layer between the green-sensitive and the blue-sensitive emulsion layer was ordered. The couplers incorporated in the emulsion layers were couplers with reactive methylene groups and phenolic coupler compounds that stfcx with p-phenylenediamine developer compounds under Formation of dyes that correspond to the complementary colors of the color sensitivity range of the individual emulsion layers corresponded, were able to react. On which the erulsions

layer-bearing side of the substrate were applied the photosensitive layers in such strength, that each support surface ² ra about 16.2 g gelatin (1500 mg / sq.ft.) accounted for. On the side of the support opposite the emulsion layers, there was a thin, blue dye.

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holding gelatin atrial layer applied.

The photographic material obtained was in Sheet form or film form exposed to a colored original and then under the conditions given below Use of an automatic one having a roller transport system Development apparatus as illustrated in the accompanying drawings and in U.S. Patent 3,025 is described, developed into a color negative * With the help of the The exposed film sample became the specified developing device having drive rollers arranged offset from one another under the following conditions successively through the specified treatment solutions and finally through a Led drying chamber:

Pre-hardening solution 38 ° C 80 seconds Neutralization solution 38 ° C 40 seconds Developer solution 38 ° C 160 seconds Stop fixing solution 38 ° C 40 seconds Washing solution 38 ° C 40 seconds Bleach solution 38 ⁰ C 40 seconds Fixing solution 38 ⁰ C 40 seconds Washing solution 38 ° C 40 seconds 2. Post-curing solution 38 ° C 40 seconds Washing solution 38 ⁰ C 40 seconds Drying chamber 49-71 ⁰ C 85 seconds

The treatment solutions used had the following composition on:

Pre-hardening solution :

The composition given for "pre-hardening solutions I, II and III" · <) π Q 8 8 7 ' ¹ ^ 9 3

Neutralization solution ;

A hydroxylamine solution, carbohydrazide solution or other aldehyde neutralization solution of the composition given in columns 4 and 5 of US Pat. No. 3,168,400.

Developer solution ;

Benzyl alcohol Sodium sulfite 5.02 G Sodium bromide Borax (pentahydrate) 1.17 G Sodium hydroxide, 50lige Sodium hexametaphosphate solution 4-Amino-N-ethyl-N- ^ ß-methane ~ 19.66 G sulfonamidoethylZ-m-toluidine- 1.88 G sesquisulfate monohydrate 33.00 G topped up with water 2.50 G 4.75 G 1 liter

pH adjusted to 10.47. Stop-fixing solution;

Part A water 7.92 g Amnoniuntthiosulfate, 58th solution 215.00 g Sodium sulfite 11.20 g Glacial acetic acid 20.00 g Sodium hydroxide 9.00 g

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part B

Water 7.20 g

Zirconyl sulfate 2.12 g

Aluminum sulfate, 25% solution 34.06 g

Parts A and B were mixed together and made up to 1 liter with water. The pH of the solution obtained was adjusted to 3.6 to 4.6 with sulfuric acid »

Bleach solution :

A solution containing potassium ferricyanide, potassium bromide and boric acid, the pH of which was adjusted to 7.9. "

Fixing solution :

An ammonium thiosulfate, sodium bisulfite and sodium sulfite containing solution, the pH of which was adjusted to 6.5.

2 »Post-curing solution :
Acid-formaldehyde solution.

The photographic recording material treated in the manner indicated delivered a high quality color negative. By pre-hardening with the aldehyde hardener solution the exposed recording material was partially cured and the swelling of the emulsion layers in the manner controlled that a color image with advantageous sensitometric Properties was obtained without the surface during the neutralization and development of the recording material

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. _22nd 192687?

surface of the emulsion layers have been deformed or damaged. The subsequent post-curing with the aid of zirconyl sulfate and aluminum sulfate containing shortstop fixing solution were further hardened the emulsion layers, the developed color image bearing so that they took in the Weiterverarbeituifg in diet provided with transport rollers automatic developing apparatus no damage, were ie neither lifted off from the substrate even discontinued . The second post-curing solution does not have to be used in all cases, but it proves to be useful in order to give the emulsion layers additional hardness and thereby facilitate the drying process.

Example 2 (comparative example)

The procedure described in Example 1 was repeated with except that no zirconyl sulfate was added to the stop-fix solution. The color negative obtained was of inferior quality, since its emulsion layers were caused by contact with the transport and guide devices of the developing apparatus and in the form of small particles on the film surface Broken particles of the emulsion layers were also found in the treatment solutions. Further It was found that the developed recording material adversely adhered to the transport rollers of the drying chamber as well as adhered to film surfaces coming into contact therewith.

Example 3 Carrying out the process with the aid of color reversal development

A photographic material as in Example 1 the type described on the one comprising the emulsion layers Side of the support per m 2 of support area approx. 15.4 g

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Gelatin (1432 mg / sq.ft.) And the one between the Containing the support and the emulsion layers arranged gray halo layer was exposed and then in sheet or roll form using an automatic developing device having a roll transport system as illustrated in the accompanying drawings or in US Pat. No. 5,027,779, developed, fixed and dried at temperatures between 32 and 52 ° C. The processing conditions were as follows and treatment solutions applied: *

Pre-hardening:

ISO seconds at 35 ⁰ C (9S ° F) using the specified pre-hardening solutions Z, II or III,

Neutralization:

1 · development;

75 seconds at 36 ° C (97 ° F) using a hydroxylamine, carbohydrazide, or other Aldehyde neutralization solution, as z. B. in columns 4 and 5 of U.S. Patent 3,168,400 will.

150 seconds at 38 ⁰ C (100 ⁰ F)

using a developing solution

of the following composition:

Sodium hexa-ketaphosphate 2.0 g N-methyl-p-aminophenol sulfate 6.0 g Sodium sulfite, anhydrous 50.0 g Hydroquinone 6.0g Sodium carbonate, monohydrate 35.0 g Potassium bromide 2.0 g Sodium thiocyanate I ₁ S g

O, continuous solution of 6-benzimidazole nitrate 12.0 el

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0.1% solution of potassium iodide made up with water

10.0 ml 1 liter

1. Stopping:

75 seconds at 38 ⁰ C (10O ⁰ F) using a stop solution of the following composition:

Sodium acetate, anhydrous 3.58 g glacial acetic acid 28.85 g

made up to 1 liter with water

To wash:

75 seconds at 32 ° C

(90 ⁰ F)

Color development:

150 seconds at 43 ⁰ C (110 ⁰ F) using a developer solution of the following composition:

Benzyl alcohol Sodium hexanetaphosphate Sodium sulfite, anhydrous Sodium carbonate, anhydrous Potassium bromide

0.1% solution of potassium iodide

Sodium hydroxide

4-Aaino-N-ethyl-N-lß-methane

sulfonamidoethylZ-e-toluidine-

sesquisulfate nonohydrate

Ethylene diaain sulfate Citric acid

t-butylamine borane

Water was added to

6.0 ml

2.0 g

5.0 g

40.0 g

0.25 g

10.0 ml

6.5 g

11.33 g

7.8 g

1.5 g

0.1 g

1 liter

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2. Stopping:

75 seconds at 43 ⁰ C (110 ⁰ F) using a stop solution of the following composition:

Sodium acetate, anhydrous

Glacial acetic acid

topped up with water

3.58 g 28.85 g 1 liter

Washed

75 seconds at 32 ^U C (9O ^U F)

Bleaching:

75 seconds at 43 ⁰ C (110 ⁰ F) using a potassium ferricyanide-potassium bromide solution, as z. As described in column 7 of U.S. Patent 3,266,895.

Fix:

75 seconds at 43 ⁰ G (11O ⁰ F) using a fixing solution of the following additives:

Ammonium thiosulphate, 58% solution 163.0 ml sodium bisulphite, anhydrous boric acid
Glacial acetic acid ...
Sodium hydroxide
'' Zirconium sulfate tetrahydrate made up with water
pH adjusted to 4.0

11 »0 g

8.0 g

19.0 ml

8.0 g

5.0 g

1.0 liter

To wash:

Seconds at 32 ⁰ C (9O ⁰ F) as well

Dry:

150 seconds at 52 ⁰ C (1 25 ° F).

90 9 88 7/1 3 9 3 '

A high quality color reversal image was obtained .. Occurred when using both roll and sheet films the emulsion layers were not damaged, the emulsion layers were firmly adhered to the support and the developed Films did not stick to each other or to the machine parts in the drying chamber. »

Correspondingly advantageous results were obtained when the zirconium salt, possibly in combination with aluminum salts, was added to the first or second stop solution. as It has proven to be expedient to add the zirconium salt to the stopper or fixing solution when using roll films When using sheet films, in addition to the zirconium salt, an aluminum sal must also be used. The usage of Aluminum salts alone led to insufficient hardening of the emulsion layers

Example 4

A color film of the type described in Example 3 was exposed and then with gradual curing and using a roller transport system having automatic Entwicaungsvorrichtung, as illustrated in the accompanying ...% drawing at about 38 ⁰ C within 10 minutes, calculated from Dry state to dry state, developed into a color negative. The pre-hardening, neutralization and color development were carried out according to the procedure described in Example 1. The described process is carried out, whereupon the developed drawing material is treated with an acidic stop bath, then washed, then treated with a bleaching solution containing ferricyanide bromide to bleach the silver present, then with the help of an acidic zirconium salt solution, the one described in Example 3 The composition would be fixed and then washed and dried. A high quality color negative was obtained which did not reveal any deformations or other damage to the emulsion layers.

9 0 9887/13 93

Claims (1)

Claims 1 «Method of making multicolor photographic Images, in particular using automatic high-speed developing devices operated at higher temperatures, according to the one intended for color photography photographic recording material consisting of a Layer support, superimposed silver halide emulsion layers and optionally intermediate and / or top layers, is exposed imagewise, whereupon in the emulsion layers of the exposed recording material, optionally after prior hardening of the layers, WMIMA *. Color images are developed and iMMI removes undeveloped silver halide and any silver images that may be present are, characterized in that the silver halide emulsion layers of the exposed recording material are before after development with the aid of a solution containing aldehyde hardening agent and after development with the aid post-cures with an acidic zirconium salt solution. 2 · The method according to claim 1, characterized in that an acidic zirconium salt solution, which also contains an aluminum salt, is used for post-hardening * 3 · Process according to claims 1 and 2, characterized in that that the exposed recording material develops into a color reversal image and the post-curing of the silver halide emulsion layers following the color development carries out 4, method according to claims 1 and 2, characterized in, that Min a photographic dye-former containing Recording material developed into a color negative and the post-curing of the silver halide emulsion layers in the 9 0 9887/1393 Follow-up to the color development *. 5. Process according to Claims 1 to 4, characterized in that the development, fixing and drying of the exposed recording material is carried out at temperatures of about 32 to 5 2 ^° C. 6. The method according to claims 1 to 5, characterized! that you have an acidic zirconium salt solution, which also K also contains an aluminum salt and a silver halide solvent as a fixing agent. 7. The method according to claims 1 to 6, characterized in * that one uses zirconyl sulfate as the zirconium salt and aluminum sulfate as the aluminum salt. 8. Process according to Claims 1 to 7, characterized in that an aldehyde hardener solution is used which as an aldehyde hardener, formaldehyde, a dialdehyde gelatin hardener or a bis-bisulfite derivative of the specified Contains dialdehyde. 9. Process according to Claims 1 to 8, characterized in that following the with the aid of an aldehyde hardener solution caused pre-hardening of the pre-hardened recording material treated with the help of an aldehyde neutralization solution. 8 8 7/13 9 3