DE2527398A1 - DEVELOPMENT PROCESS FOR LIGHT-SENSITIVE, PHOTOGRAPHIC SILVER HALOGENIDE MATERIALS - Google Patents

Description

Development process for silver halide photographic light-sensitive materials

The invention relates to a new process for developing silver halide photographic light-sensitive materials. More particularly, the invention relates to a new method of developing photosensitive photographic materials Silver halide materials, which is characterized in that light-sensitive, photographic silver halide materials, containing a photographic coupler and a reduced amount of silver, developed with a solution containing hydrogen peroxide, whereby enhanced color images are obtained.

Silver halide photographic light-sensitive materials have high photosensitivity and excellent Ability to give pictures and thus are widely used. For some time now the global shortages have been playing silver deposits and the increase in the cost of raw materials play a role. This will result in great industrial Difficulties, especially with photographic, photosensitive Silver Halide Materials Requiring Large Amounts of Silver · There is therefore a need for the development of methods to overcome these difficulties. To meet the above mentioned need, silver halide photographic light-sensitive materials capable of saving silver have been proposed, and various processes for the production of such photo-

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graphic materials known. For example, in the published Japanese patent application 13576/74, a method is described in which a coupler of the so-called 2-equivalent type is used, which is prepared by introducing a substituent into an active position of the color coupler so that the amount of silver, which is required to form 1 molecule of dye, and which used to be 4 atoms, can be reduced to two atoms. According to the known method, the theoretical amount of silver used is reduced to half that required when a known 4-equivalent type coupler is used, and in practice it is possible to reduce the amount of silver to less than to reduce half the amount required of the 4-equivalent type coupler because the 2-equivalent type coupler has a better efficiency of utilizing the silver than the 4-equivalent type coupler. When such a method is used, however, "the upper limit of the amount of silver that can be reduced approximately vm a Drit.tel, compared to the amount that is required at the time, reduced; a further reduction in the amount of silver cannot be expected.

In terms of the developed silver you get when a light-sensitive, photographic silver halide material is exposed imagewise and then developed, a so-called image intensification method was proposed in which an oxidation product from a developing agent by the use of the silver as a catalyst is made more effective, resulting in a high-density color image. Corresponding In this process, the developed silver can be used repeatedly many times, so that color images with good Effectiveness can be obtained and the amount of silver can be reduced to a great extent.

A typical method for image enhancement of photosensitive, silver halide photographic materials

for example the process described in GB-PS 1,268,126, in which the images are made using peroxy compounds and the method described in Japanese Patent Application Publication 9728/73 which the color images are enhanced by taking advantage of the beneficial catalytic effects of cobalt complexes. A similar method for enhancing color images is described by J.S. Friedman on page 406 of the book "History of Color Photography "(1956) published by American Photographic Publishing Co., which Color image enhancement is done using hydrogen peroxide and p-phenylenediamine. In all of these procedures The densities of the images are effectively increased and these methods are thus quite effective methods of adding silver save or not attack the silver reserves. It is, however, a fact that these procedures are not yet in use Practice to be used. The most likely reason for this is that the developing baths used in these processes have an extremely low storage stability or storability.

It is known that hydrogen peroxide and hexavalent cobalt (III) complex salts are typical oxidizing agents for reinforcement of color images, and obviously the effects of hydrogen peroxide are better. Despite the fact, that hydrogen peroxide has long been well known as an oxidizing agent becomes a process in which hydrogen peroxide is not used in practice. This is due to two major disadvantages of this process, namely that it is pronounced in the photographic materials Fog occur and that the amplification ratio is unstable, i.e. not reproducible. The term "boost ratio", as used herein means the ratio between the maximum density taken as 1 obtained when the photographic material is exposed and developed in the usual way, and the maximum density that is obtained when the photographic ma-

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material is exposed in the same manner as described above and then subjected to gain development. Around To overcome these disadvantages, methods have been proposed in which chelating agents or stabilizers are combined be used with hydrogen peroxide. In these processes, the development baths can cause development if the operating time is within a week. If their operating time is longer, there are great disadvantages to it not only veils are formed and the maximum density

(D _m ") decreases considerably, but the development max

The processing time that is required for a defined amplification ratio is also greatly increased.

On the other hand, there are hexamine cobalt trichloride or the like Hexavalent cobalt (III) complex salts are used, the strengthening ability of the developing bath is within a If it is lowered for a short time such as 3 hours in extreme cases, and if the bath is left to stand for about 2 weeks, then form severe fog in the photographic material developed therewith, even if the developing solution is completely covered with nitrogen gas. To these disadvantages To eliminate this, many improvements have been made. In terms of practicality, these are improvements but only small improvements.

The applicant has carried out attempts to find an image intensification method that can be used in large-scale paint laboratories for long periods of time.

The present invention is therefore based on the object of providing a new process for the development of photographic, to provide silver halide photosensitive materials which do not have the aforementioned disadvantages and which do hydrogen peroxide, which has a great oxidizing power compared with other oxidizing agents, as an oxidizing agent is used for the oxidation of color developing agents in the presence of the imagewise developed

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Silver of the photographic material as a medium, wherein Color images with increased amplification ratio can be formed

According to the invention, a method is to be created to the images of silver halide photographic light-sensitive materials to reinforce that there is no or practically no environmental pollution, especially in waste water, results.

Thus, the present invention seeks to provide a method in which silver halide photographic light-sensitive materials can be developed using a bath containing hydrogen peroxide with a very simple composition and wherein the photographic materials give excellent color images without fog and without lowering the maximum density even if the development is carried out for a long time will.

The present invention seeks to provide a color image enhancement method capable of obtaining excellent color images when using silver halide photographic light-sensitive materials used with reduced amount of silver.

Research continued to determine the reasons determine why the image intensification method using hydrogen peroxide causes fog so quickly are formed and the amplification ratio is not reproducible.

As a result, it was found that one of the reasons is the excessive accumulation of the developing agent in the bath containing hydrogen peroxide. It has further been found that the delivery of the developer into the bath containing hydrogen peroxide _{gives such advantages as an increase in the D m} _ value and a reduction in the development time,

UIcLn.

that the strengthening bath, however, when the developing

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agent accumulates in a larger than a certain amount, has very different properties and that it is very difficult to obtain stable photographic images when it is used. Furthermore, it was found that the formation of fog takes place more easily when the amount of silver is stoichiometrically greater than that of the coupler used, and this phenomenon is particularly dependent on the pH of the developing bath. Due to the The above fact is the use of silver halide photographic light-sensitive materials which decreased one Amount of silver contained, in the present invention of advantage, which is detailed in the following examples is explained.

Based on the above findings, it has been found that the inventive Object can be achieved if one uses a method in which light-sensitive, photographic Silver halide material containing silver and a photographic coupler in an amount which is at least 50%, stoichiometrically, is higher than that of the Silver in the silver halide, is developed with a developer containing a developing agent, and then is treated with a solution containing hydrogen peroxide, the treatment being carried out continuously and the solution is essentially devoid of developing agent. It is thus possible to make an image stable or reproducible and continuously boosting for long times using hydrogen peroxide, a method of which has been assumed in the past that it must be possible, but that it would be difficult to do if a silver halide photographic light-sensitive material, contains the silver halide and a photographic coupler in an amount which is at least about 50% is stoichiometrically greater than that of the silver in the silver halide, with a hydrogen peroxide containing Bath developed the concentration of the developing agent, which is introduced by entrainment, exactly

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_ ₇ _ 2527399

is trolled so that it is continuously under a certain Limit is kept.

The expression "that the processing or development is carried out continuously while the solution is essentially is free of development agents "does not mean that in There is no developing agent at all in the bath containing hydrogen peroxide, it just means that it does Developing agent, which is brought into the bath together with the photographic material during operation, for the image intensification is used and that the development is carried out continuously while the concentration of the developing agent, which is introduced into the bath by entrainment, is always regulated so that it is below a certain value. The description should therefore be interpreted in such a way that during the development or the Processing the developing agent locally in high concentrations only within the photographic material the bath or in close proximity thereof and that the concentration of the developing agent in others Places than within the photographic material or in close proximity to it continuously below such Concentration is maintained at which no adverse effects on the photographic properties (e.g. the Fogging and photographic density stability) or developing performance (e.g., the Development time and similar properties required to obtain the same photographic properties to achieve) of the actually formed photographic image. The critical concentration of the developing agent in the hydrogen peroxide bath varies more or less less depending on the kind of silver halide photographic light-sensitive material used, the kind the developing agent and the type and concentration of the additives other than hydrogen peroxide in the hydrogen peroxide containing bath. It is preferable to adjust the concentration of the developing agent in the hydrogen peroxide bath

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to be controlled so that it does not exceed 2/1000 moles when a photographic material in the present invention is developed in a system in which a p-phenylenediamine type compound is used as a developing agent and a hydrogen peroxide bath containing no additives other than hydrogen peroxide can be used. this is a typical embodiment of the present invention.

According to the most preferred embodiment of the invention, the hydrogen peroxide-containing bath does not need any additives such as chelating agents, stabilizers, etc., and the development can be carried out effectively, by using a solution that contains only hydrogen peroxide alone. Accordingly, not only the The release of organic compounds into the waste water is kept to a minimum, but the outflowing hydrogen peroxide decomposes oxidatively harmful organic compounds, and can be used in the treatment of waste water from the laboratory thus still achieved great advantages.

So that the hydrogen peroxide bath is essentially of developing agent remains free, the bath must be supplemented with hydrogen peroxide in an amount greater than sufficient according to the amount of developing agent transferred to the bath.

The concentration of the hydrogen peroxide bath used in the present invention varies depending on the Type of photographic material used, the type of Developing agent and the process implementation like the

. but it usually lies

in the range from 0.1 to 40% by weight, preferably generally im Range from 0.3 to 12% by weight. The concentration and the crowd of additional solution can be appropriately selected so that the concentration of hydrogen peroxide in the bath does not vary and the concentration of developing agent in the bath does not exceed the critical value.

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In the present invention is advantageously a silver halide photographic light-sensitive material containing a silver halide and a photographic coupler in an amount which is at least 50% stoichiometric is greater than that of the silver in the silver halide. Examples of silver halides used in the Silver chloride, silver bromide, silver iodide and mixed silver halides can be used in the present invention such as silver chlorobromide, silver iodobromide and silver iodochlorobromide. Emulsions of these silver halides can be prepared by known methods. For example For example, the silver halide emulsion used in the present invention may be a so-called reverse emulsion, a Lippmann emulsion or a covered grain emulsion which has been tarnished either optically or chemically beforehand, and the emulsion is suitably prepared, depending on the kind and use of the resulting photographic material, selected. The type, halogen content and proportion, average particle size and size distribution of the silver halide emulsion are also made according to the kind and use of the corresponding photographic Materials selected. For example, an emulsion mainly containing silver chloride becomes a very has a small particle size or is very fine and has a narrow size distribution for the production of photographic material is used, which has a relatively low speed and high image quality, whereas an emulsion having a relatively large particle size and a lower silver chloride content is used for photographic material which should have a relatively high speed. An emulsion that has previously been tarnished is used for the manufacture of photographic material of the type used for direct positives. These Silver halide emulsions can be chemically produced using active gelatin, sulfur sensitizers, e.g. allyl thiocarbamide, Thiourea and cystine, selenium sensitizers or precious metal sensitizers, e.g. gold sensitizers

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such as potassium aurithiocyanate, potassium chloraurate and 2-aurosulfobenzothiazole methochloride be sensitized or they can be sensitized by sensitizers that water · ^ contain soluble salts of ruthenium, rhodium and iridium such as ammonium chlorpalladate, potassium chloroplatinate and Sodium chloropalladite (some of which act as sensitizers or anti-fogging agents, depending on their amounts) either alone or in suitable mixtures (e.g. one can use a gold sensitizer with a sulfur sensitizer or mixtures from gold sensitizers with selenium sensitizers). These silver halide emulsions can also be optically sensitized for the desired wavelength ranges by using optical sensitizers, e.g. cyanine or merocyanine dyes such as zeromethine-j monomethine Dimethine or trimethine dyes.

The silver halide is dispersed in a suitable protective colloid to form the photosensitive layer. As Protective colloids for the photosensitive layer and other layers, e.g. inner layer, protective layer and filter layer, gelatin is generally used. In addition, one can use gelatin derivatives, colloidal albumins, cellulose derivatives or synthetic resins such as polyvinyl compounds, e.g. polyvinyl alcohols, use. These are used either alone or mixed together. Acetyl cellulose can also be used with an acetyl content of approximately 19 to 26% or water-soluble ethanolamine cellulose acetate be used with it.

The photosensitive, Silver halide photographic materials contain couplers for the formation of the color images. Examples of Useful couplers are yellow couplers of the open-chain methylene type, magenta couplers and magenta couplers 5-pyrazolone type, and cyan or cyan couplers of phenol or Naphthol type. These couplers may be so-called · 2-equivalent type or 4-equivalent type couplers, and they

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may be used together with colored couplers of the azo type, compounds of the osazone type or couplers of the type used in the Development are diffusible and result in dyes, as used for car masking or car shifting. In this case, it is desirable to do the above Masking or displacement couplers together with so-called color couplers that are colorless before color development. For a further enhancement of the photographic Properties of the photographic materials so-called competing couplers, DIR '(development inhibitor release) Coupler and BAR (bleach accelerator release) coupler included along with other couplers.

The yellow couplers are open-chain ketomethylene compounds used. For example, effective pivalylacetanilide-type yellow couplers are those compounds disclosed in French Pat

1 291 110 are described, and effective yellow couplers des Benzoylacetanilide-type are the compounds found in the Published Japanese Patent Application 19031/71 and U.S. Patent 2,875,051. Furthermore are effective Yellow couplers the active-position O-allyl-substituted Couplers as described in U.S. Patent 3,4-08,194 the active position O-acyl substituted couplers, such as them in U.S. Patent 3,447,928, the active positional hydantoin compound substituted Couplers as described in Japanese Patent Application Laid-Open No. 29432/73 substituted for the active positional urazole compound Couplers as described in Japanese Patent Application Laid-Open No. 66834/73 are the active ones Positional succinic acid imide compound substituted couplers as disclosed in published Japanese patent application 13576/74, the active-positional monooximide compound-substituted Coupler that is in the DT-OS

2,433,812, the active-position pyridazone compound substituted Couplers as described in Japanese Patent Application Laid-Open No. 10736/74, the active position fluorine substituted couplers such as

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they are described in GB-PS 94 490, the active position chlorine or bromine-substituted couplers as described in GB-PS 780 507 and the active-position-O-sulfonyl-substituted ones Couplers as described in GB-PS 1,092,506, the so-called 2-equivalent type couplers are. Of these yellow couplers, particularly preferred are those disclosed in U.S. Patent No. 3,408,194, Laid-Open Japanese Patent Application 29432/73, DT-OS 2,433,812 and Japanese Patent Application Laid-Open 66834/73 will.

The magenta couplers used in the present In the present invention are compounds of the pyrazolone type, the pyrazolotriazole type, the pyrazolinobenzimidazole type and the indazolone type. Preferred of these Pyrazolone-type magenta couplers are the compounds disclosed in U.S. Patents 3,127,269, 2,600,788, 3,519,429, 3,419,391, and US Pat 3 0.63 653, GB-PS 1 342 553, DT-PS 2 162 778, the published Japanese Patent Application 29639/74 and U.S. Patent 3,684,514. Preferred purple couplers of the pyrazolotriazole type are those described in DT-PS 1,810,464 and in BE-PS 792 525; preferred Pyrazolinobenzimidazole type magenta couplers are those published in U.S. Patent 3,061,432 issued to Japan Patent application 60479/71 and in DT-PS 2 156 111 are described, and preferred purple couplers of the indazolone type are those described in BE-PS 769 116. Of these, they become particular in the present invention preferably the magenta couplers described in US Pat. No. 3,684,515 and the 3-anilinopyrazolone magenta couplers, described in U.S. Patent 3,127,269 is used.

Useful cyan couplers used in the present invention are the phenolic compounds such as they are described, for example, in U.S. Patents 2,423,730, 2,801,171 and 2,895,826 and in BEP 779,512; the active ones Position-O-aryl-substituted naphtho! Compounds, such as them

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. ₁₃ - 2f27398

in U.S. Patent 2,474,293 and British Patent 1,084,480 and the phenol and naphthol compounds as disclosed in Japanese Patent Application Laid-Open No. 37425/72, DT-OS 2 424 946 and DT-OS 2 520 820 and in German patent application P 25 04 844.6.

As colored purple couplers, one can use colorless purple couplers which have active positions which are determined by arylazo- or heterozylazo compounds such as those described in U.S. Patents 3,005,712, 2,983,608, 2,801,171 and 3,684,514 and in GB-PS 937,621.

The colored cyan couplers can be active-positional aryl azo-substituted ones Use couplers as disclosed in U.S. Patent Nos. 3,034,892, 2,521,908 and 3,811,892, and in British Patent 1,555 and as the masking coupler one can use one of the type in which the dye is in the developing baths by reaction with the oxidation products of the developing agent flows and that in DT-OS 2 424 946, the German patent application P 25 04 844.6 and in GB-PS 1 084 480 are described.

Competing couplers may include, for example, citrazinic acid and similar compounds described in U.S. Patent 2,742,832 and the couplers described in DT-PS 1,155,676 can be used as the white coupler.

The silver halide emulsion which is a photographic coupling contains, in an amount that is at least 50% stoichiometrically greater, based on the silver, and the was prepared in the above manner, is applied as a layer on a carrier, optionally together with a Underlayer, an intermediate layer, a filter layer, an anti-curl layer, a protective layer, etc., wherein the silver halide photographic light-sensitive material used in the present invention. Examples of support materials used in this

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are paper, laminated papers (e.g. a laminate of polyethylene and paper), sheet glass, and films or films made from substrates such as cellulose acetate, cellulose nitrate, polyesters, polycarbonates, polyamides, polystyrenes and polyolefins. In order to improve the adhesion of the individual layers thereof, the surfaces can the carrier materials are treated in different ways, for example they can be saponified with Corona discharge treated, treated with base or provided with a coating, hardened etc.

Basically, a photographic material contains at least one support and, applied to it, a photosensitive one Layer. However, as previously mentioned, it generally has suitable layers in various positions and positions consists of more than a few layers. The photosensitive layer itself may be made of a laminate such as a A layer containing a silver halide at a relatively high speed; and a layer containing a silver halide at a relatively low speed, and that for the same or different wavelength ranges has been color sensitized.

The photographic material used in the present invention can contain various photographic additives in the photosensitive layer and / or in the other layers, e.g. in the intermediate layer, the underlayer, the filter layer, the protective layer and the image receiving layer, contain. Examples of such photographic additives are stabilizers, e.g. mercury compounds, Triazoles, azaindenes and quaternary benzothiazolium, zinc or cadmium salts; Sensitizers like quaternary ammonium salts or polyethylene glycols; Agents which improve the film properties, e.g. glycerine, dihydroxyalkanes such as 1,5-pentadiol, ester of ethylene-bis-

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glycolic acid, bis-ethoxy diethylene glycol succinate, amides of acrylic acid type and polymer dispersions; Hardener, e.g. Formaldehyde, halogen-substituted fatty acids such as mucochloric and mucobromic acids, compounds with acid anhydride groups, Dicarboxylic acid chlorides, disulfonic acid chlorides, biesters of methanesulfonic acid, sodium bisulfite derivatives of dialdehydes, whose aldehyde groups have 2 to 3 carbon atoms separately are bisaziridine and ethylenimine; Carriers, e.g. saponin, lauryl or oleyl monoethers of Polyethylene glycols and sulfated and alkylated polyethylene glycol salts; Coating auxiliaries, e.g., sulfosuccinic acid salts; organic solvents, e.g. coupler solvents (high- and / or low-boiling organic Solvents such as dibutyl phthalate, tricresyl phosphate, acetone, methanol, ethanol and ethylene cellosolv); and so-called DIR compounds, which give color development inhibitors at the time of color development and at the same time are essentially colorless Form compounds, and additives such as antistatic agents, release agents, ultraviolet absorbers, fluorescent brighteners, anti-slip agents, matting agents, and antihalation agents or anti-irradiation agents. These additives can either be used alone or in a mixture can be used from two or more compounds.

The photosensitive, photographic Silver halide materials used in the present invention can be used successfully in many fields and they are used, for example, as general negative photographic materials, general photographic Reversal materials, as general positive photographic materials, as photographic materials of the direct positive type and as photographic materials for specific ones Uses (e.g. for printing, for X-rays, for high resolution, for infrared, ultraviolet, etc.).

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After exposure, the photosensitive, photographic Silver halide materials used in the present invention color-developed with a developer, which contains a color developing agent as a main component. Typical examples of color developing agents that are preferably used in the present invention, compounds of the p-ethylenediamine type such as diethyl-pphenylenediamine hydrochloride, Monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5 »(N-ethyl-N-dodecylamino) toluene, N-ethyl-N-ß-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-ß-methanesulfonamidoethyl-4-aminoaniline, 4-N-ethyl-N-ß-hydroxyethylaminoaniline, 4-amino-3-methyl-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-ß-hydroxyethylaniline sulfate, 4-Amino-3-ß- (metiiansulfonamido) -ethyl-N, N-diethylaniline and 4-amino-N- (2-methoxyethyl) -m-toluidine. These color developing agents can be used either alone or as a mixture of two or more multiple connections can be used or if desired they can be used in conjunction with a black and white developing agent such as hydroquinone. The color developer contains further generally an alkaline agent such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfate or sodium sulfite and may contain various additives such as an alkali metal halide such as potassium bromide and a dye contain regulators such as citrazinic acid.

For a particular diffusion transfer process, the color developer described above is incorporated into the image receiving material. It is also with this procedure possible to operate with the photographic material first either a color developing agent or a Contains alkali agents and then is developed with the other at the time of development.

The photographic material color-developed in the manner described above is then either as it is, or after simply washing (rinsing) it with water,

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in a manner according to the invention with a containing hydrogen peroxide Bathroom further developed or treated further. Optionally, the photographic material can be a pre-hardening treatment and a pre-bath treatment are subjected for a better impregnation with the color developing agent, and in the case of reversal development, it is subjected to black and white development, bleaching and so on. If that If silver halide or the developed silver is to be removed from the system, treatment is carried out using a fixing solution, either alone or together with a bleach solution, or it becomes a bleach-fix solution commonly used. This treatment is carried out along with the other various treatments, such as with water washing, fixing and stabilizing. A solvent for silver halide is used as the fixing component such as sodium thiosulfate or ammonium thiosulfate, whereas as a bleaching component potassium ferricyanide, iron (III) ammonium ethylenediamine tetraacetate or sodium salt can be used.

Typical concrete examples of treatment steps which are carried out in the development or processing method according to the invention can be used are given below; however, this is not intended to be a limitation.

(1) color development - enhancement - bleach-fix washing with water - stabilization;

(2) color development - pre-bath - reinforcement - washing with water - stabilization;

(3) Pre-curing - primary black and white development, bleaching - washing with water - secondary exposure - color development - reinforcement - bleaching, fixing - washing with water - stabilization;

(4) Color development - rinsing - amplification - fixing - washing with water - stabilization;

(5) color development - amplification - washing with water,

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The following examples illustrate the invention.

example 1

Both sides of a polyester film are subjected to a corona discharge treatment and then to a basic treatment. Then one side of the polyester film base material is coated with a mixture containing a panchromatic color-sensitized silver iodobromide emulsion and a dispersion which is prepared by gently dispersing in an aqueous gelatin solution a solution which is prepared by adding an equivalent in dibutyl phthalate Dissolves amount of 1- (2,4,6-trichlorophenyl) -3- [3- (2,4-di-tert-phenylphenoxy-acetamido) -benzamido] -5-pyrazolone. The coated amounts of coupler and silver per 100 cm are 7.0 mg and 1.84 mg, respectively. The other side of the polyester film base material is then coated with a mixture containing a panchromatically color-developed silver qodbromide emulsion and a dispersion which is prepared by adding a 3.7: 3 mixture of 2- ( 2,4-Dioxo-3,3-di-n-propylazetidin-1 -yl) -2-pivaclyl-2'-chloro-5 ^f - [4- (2,4-di-tert -pentylphenoxy) -butanamido ] -acetoanilide and 1-hydroxy-N- [4- (2,4-di-tert-pentylphenoxy) -butyl] -2-naphthamido gently dispersed in tricresyl phosphate. The coated amounts of yellow coupler, cyan coupler and silver per 100 cm are 5.55 mg, 4.5 mg. and 2.75 mg, respectively.

The X-ray color photographic material thus obtained is exposed through a fluorescent intensifying screen and an aluminum wedge to X-rays for 0.5 minutes at a tube voltage of 60 KV and a current of 200 mA, and then developed at 24 ^° C. for 7 minutes with a developer of the following composition .:

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15th ml 5 ε O , 5 g 2 G 5 G 30th G 4th , 5 g 1 1

Benzyl alcohol Potassium sulphite Potassium bromide Hydroxylarain sulphate

4-Amino-N-ethyl-N- (ß-hydroxyethyl) -m-toluidine sulfate

Potassium carbonate

Ethylenediamine tetraacetic acid ■ water up to
(pH 10.1)

Immediately thereafter and without washing with water, it was developed photographic material at 24 ° C for 5 minutes immersed in a strengthening bath of the following composition:

Hydrogen peroxide (35%

aqueous solution) 10 ml

Water up to 11

Subsequently, the photographic material was washed well with water and then subjected to the usual bleaching, fixing and cleaning agents Conducted stabilization baths, as used in general color photography, whereby an X-ray color image is obtained became. The X-ray color image thus obtained is a color image and contains a lot of information. The amount of used Silver is approximately 1/30 of the amount of silver used in the prior art.

Example 2

A solution of a 2- [2- (2,4-di-tert-pentylphenoxy) butanamido] -4,6-dichloro-5-methylphenol coupler in dibutyl phthalate is gently dispersed in an aqueous gelatin solution in order to produce a coupler dispersion. This dispersion is mixed with a silver chlorobromide emulsion and the resulting mixture is coated onto a resin Paper backing applied and then dried to obtain a sample. The amounts of coupler and silver applied are varied as indicated in Table I.

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- 20 Table I.

Sample silver _p coupler _p

(mg / 100 cnr) (mg / 100 cm)

A (photographic not according to the invention Material) 3.0 2.9

B (photographic material not according to the invention) 1.5 2.9

C (inventive photographic Material) 0.75 2.9

These samples are individually cut and processed into rolls and then exposed with an automatic printer and then developed with an automatic developing machine. The development speeds and orders are the following:

Color Development (4 minutes) - Enhancement (4 minutes) - Wash] with water (1 minute) - bleach-fix (1.5 minutes) washing with water (2 minutes) - stabilization (1 minute) rinsing - Dry.

All process steps are carried out at 30 ⁰ C, except for the water-washing and rinsing stages. The compositions of the developing solutions are as follows:

Color developer

Benzyl alcohol 5.0 ml ■ Sodium hexamethapho sphat 2.5 g anhydrous sodium sulfite 1.85 g Potassium bromide 0.50 g Sodium bromide 1.40 g borax 39.1 g N-ethyl-N-ß-methanesulfoamidoethyl 4-amino-3-methylaniline sulfate 5.0 g Water up to (pH 10.3)

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- 21 - Reinforcement solution 2527398 The received 38% hydrogen peroxide solution Water up to 10 ml Bleach-fix solution 1 1 Iron ammonium ethylenediamine tetraacetate Ammonium thi ο sulfate 61.0 g Sodium metabisulfite 124.5 g anhydrous sodium sulfite 13.3 g Diammonium ethylenediaminetetraacetate 2.7 g Water up to 5.0 g (pH 6.5) 1 1 Stabilization solution Glacial acetic acid water 20 ml Sodium acetate up to 800 ml Water up to pH 4.5 Ms 4.0 1 1 The supplementary amounts for each color developer that The bleach-fix solution and the stabilizing solution 15 to 16 ecm per chamber (12 cm χ 16.5 cm) and excess Developing solutions were taken out as an overflow. The too additional amount of reinforcement solution were two values like 1.5 to 16 ecm and 30 to 35 ecm per chamber. Results are given in Table II.

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ο co ex »

O CD O

Operating ³ W Table II A. Max ^D min Color images Max C. D.
Max I.
ro
ι Reinforcement days 0.08 2.52 0.08 B. 1.58 ^D min 1.20 ro Bathroom additional - 0.10
0.31
0.73 Densities of 2.60
2.55
2.64 0.10
0.23
0.55 2.63
2.51
2.31 0.08 2.61
2.32
2.22 ro lot
(ccm / chamber) 0
7th
14th 0.10
0.25
0.54 2.60
2.75
2.75 0.10
0.22
0.52 2.63
2.64
2.72 0.09
0.10
0.23 2.61
2.62
2.61 co
CD not used 0
7th
14th 0.09
0.09
0.09 ver
wen- 15
det ver
wen- 30
det

From Table II it can be seen that if the sample according to the invention is developed according to the developing method of the present invention, an excellent high-D image

Max

and low fog even if the development is carried out in continuous operation for a long time will. It can also be seen that the developing method of the present invention is particularly effective when the amount of coupler is greater than the amount of silver, and thus with success in developing photographic materials can be used with reduced silver content. The reinforcement bath according to the invention shows surprising effects, although it contains only hydrogen peroxide alone, and because of its ease of manufacture, economy and the low contamination of the bath, the development process according to the invention is better than the known development processes .

The developing bath according to the invention can of course contain stabilizers, chelating agents, preservatives etc. as required as required. if however, the developing solution contains a complex composition, not only does it become difficult to prepare, but also if it is stored for a long time, its stability deteriorates. Experiments by the applicant have shown that the properties of developing solutions deteriorate very much if they are longer than can be kept for a week and are therefore disadvantageous for continuous operation for a long time in practice. The properties of the developing solutions are also dependent on the pH values, so that it is necessary is to precisely regulate the pH of the developing solutions. In contrast, if is a simple hydrogen peroxide solution used as a development solution for reinforcement, not just the work required for manufacture of the developing solution is minimal, but also no control of the pH value of the solution is required, so that the developing solution with benefits without

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Difficulties can be established.

Example 3

A solution of a 2- (1-benzyl-2,4-dioxoimidazolidin-3-yl) -2-pivalyl-2 «-chlor-5 '- [4- (2,4-di-tert.-phentylphenoxy) - butanamidoj-acetanilide coupler in dibutyl phthalate is gently dispersed in an aqueous gelatin solution to produce a coupler dispersion. This dispersion is mixed with a silver chlorobromide emulsion and the resulting mixture is coated on a resin-coated paper support to form a layer on the support. The coated amounts of the coupler and silver are 8.23 mg and 1.00 mg per 100 cm ^2, respectively. An intermediate gelatin layer containing dioctyl hydroquinone is then formed on top of this layer. On this intermediate layer, an ortho layer is also formed which contains a mixture of a green-sensitive silver chlorobromide emulsion and a coupler dispersion which is prepared by adding a solution of a coupler, namely 3- £ 2-chloro-5- [ (1-octadecenyl) succinimido] anilinoj -1- (2,4,6-trichlorophenyl) -5-pyrazolone, gently dispersed in dibutyl phthalate. The amounts of coupler and silver used in this ortho layer are 4.3 mg and 1.15 mg per 100 cm ² , respectively. This ortho-layer is then coated with a gelatin solution of dioctylhydroquinone to form a layer that prevents color clouding. A panchromatic layer is also formed on this layer which contains a mixture of a red-sensitive silver chlorobromide emulsion and a coupler dispersion which is prepared by adding a solution of a coupler, namely 2- [2- (2,4-Di -tert-pentylphenoxy) -butanainido] -4,6-dichloro-5-methylphenol, gently dispersed in dibutyl phthalate. A gelatin protective layer is formed on the panchromatic layer thus formed, and then an ultraviolet absorbing layer containing an ultraviolet absorbent is formed to obtain a color photographic paper material. The quantities

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of couplers and silver that are in the panchromatic layer

were used are 2.9 mg and 0.85 mg per 100 cm, respectively. The photographic material thus obtained is divided into three samples, a first, a second and a third sample.

The first sample is exposed through a negative color film and then in the usual way as described in Example 2 with the exception that the additional solution for each chamber was varied to 30 ecm. In the finished prints no changes were observed at all, even during a month's operation, and it was found that an excellent color print is very stably obtained from the color photographic material with a smaller amount of silver could be.

example

A mixture of 1-hydroxy-N- [4-2,4-di-tert-pentylphenoxy) butyl] -2-naphthamide (10.1 mg / 100 cm ² ), 4- (2-ethoxycarbonylphei ylazo) - 1-hydroxy-N- [4- (2,4-di-tert-p entylphenoxy) butyl] -2-naphthamide (3.2 mg / 100 cm ² ) and 1-oxo-2- (1-phenyl 5-tetrazolylthio) -6- (2,4-di-tert-pentylphenoxyacetamido) -

indan (4.3 mg / 100 cm) is dissolved in Tricresy! phosphate. the resulting solution is divided into two equal parts, a first and a second solution.

The first solution is gently dispersed in aqueous gelatin solution, a coupler dispersion being obtained. This dispersion was made with a high speed red sensitive silver iodobromide emulsion (Ag 2.5 mg / 100 cm) mixed and the resulting mixture was on a transparent Cellulose triacetate base film applied to form an emulsion layer on the film base.

An inner layer comprising a gelatin solution of 2,5-di-tert-oetyl-hydroquinone was formed on the emulsion layer thus formed contained. On this inner layer was

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then an ortholayer was formed which contained a mixture of a green-sensitive silver iodobromide emulsion (Ag 1.8 mg / 100 cm) and an Euppler dispersion, which is prepared by adding a solution of 1- (2,4,6- TrichloiT3henyl) -3- [3- (2,4-di-tert.-penty! Phenoxyacetamide) benzamido] -5-pyrazolone (10.2 mg / 100 cm), 1- (2,4,6-trichlorophenyl) - 3- [3- (2,4-di-tert-pentylphenoxyacetamido) -benzamido] -4- (4-methoxyphenylazo) -5-parazolone (2.2 mg / 100 cm) and 1-oxo-2- (1 -phenyl-5-tetrazolylthio) -6- (2,4-di-tert.-pentylphenoxyacetamide) -indane (0.6 mg / 100 cm in dibutyl phthalate. A yellow filter layer of colloidal silver was formed on this ortho layer On this filter layer was further formed as a top layer a layer of a mixture containing a high-speed blue-sensitive silver iodobromide emulsion (2.0 mg / 100 cm) and a coupler dispersion which had been prepared ird by adding a solution of 2- (1-benzyl-2,4-dioxoimidazolidin-3-yl) -2-pivaloyl-2 ^f -chlor-5 ^f - [2- (3-pentadecylphenoxy) butanamido ] -acetanilide (25 mg / 100 cm) gently dispersed in dibutyl phthalate. A protective gelatin layer was then formed on this uppermost layer.

In the above manner, two negative photographic materials A and B were prepared.

Photographic material A became a 35 mm roll of film cut in 20 frames, exposed and then developed using an automatic developing device of the hanging type used. The following order and times are used in the development stage:

Color development (3 * 15 ") - reinforcement (3 ^f 15") - bleaching (6 ^f 30 ") - washing with water (3'15 ¹ O - fixing (6 * 30«) washing with water (3 ^r 15 ^M ) - Stabilization (1 «30»).

The compositions of the individual developing solutions are the following:

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- 2? - developer 2527398 Fixing solution 1 1 anhydrous potassium carbonate Ammonium thio sulfate (70% aqueous anhydrous sodium bicarbonate 26.0 g Solution) 100 g Potassium sulfite (dihydrate) 3.5 g anhydrous sodium sulfite 10.0 g Potassium bromide 18.0 g Sodium metasulfite 150 g Sodium chloride 1.3 g Water up to 10.0 ml Sodium nitrilotriacetate monohydrate) 0.2 g (pH 6.0) 1 1 Potassium hydroxide 2.0 g Hydroxylamine sulfate 0.4 g 4-amino-3-methyl-N-methyl- (ß-hydroxy- 2.0 g ethyl) aniline sulfate 175.0 ml Water up to 5.0 g 8.6 g (pH 10.5) 1 1 • 2.3 g Reinforcement solution 1 1 38% aqueous hydrogen peroxide solution 25 ml Water up to Bleach solution Iron ammonium ethylenediaminetetraacetate Diammonium ethylenediamine tetraacetate Ammonium bromide Glacial acetic acid Water up to (pH 6.0)

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Stabilization solution

Formalin (37? Ige aqueous solution) 1.5 ml

Konidax (made by Konishiroku

Photo Industry Co., Ltd.) 7.5 ml

Water up to 11

All stages were performed at 38 ⁰ C with the exception of washing stages with V / ater.

In this experiment, it is found that a satisfactory image is not obtained when the photographic material is used is not passed through the strengthening bath, and that the D__ value is then about 1.1, whereas if the photographic material is passed through the intensifying bath, a satisfactory image can be obtained and the D_ "value reaches 2.5 to 3.0. During operation will each developing solution with the exception of the amplification solution with 15 ecm additional solution per 35 mm film roll with twenty Supplemented film images, and the reinforcement solution is supplemented with 40 ecm additional solution per roll. One poses states that the developing solutions have no adverse effects on the resulting images even if the operation takes place during one month and if more than 100 rolls are developed per day.

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Claims (1)

Claims rl Process for the development of light-sensitive, photographic silver halide materials, characterized in that a light-sensitive, photographic Silver halide material containing a silver halide and a photographic coupler in an amount which is stoichiometrically greater by at least 50%, based on the silver in the silver halide, developed with a developer containing a developing agent, and then is developed or treated with a solution containing hydrogen peroxide. 2. A process for developing silver halide photographic light-sensitive materials, characterized in that a silver halide photographic light-sensitive material containing a silver halide and a photographic coupler in an amount which is at least 50% stoichiometric greater than the silver in the silver halide , is developed with a developer containing a developing agent and then subsequently developed or treated with a solution containing hydrogen peroxide, the solution being kept substantially free of the developing agent. 609882/0906