DE2009078A1 - Diffusion transfer photographic process and photographic material for carrying out the process - Google Patents

Description

EASTMAN KODAK COMPANY, 343 State Street, Rochester State New York, United States of America

Photographic diffusion transfer process as well photographic material for carrying out the process

The invention relates to a photographic diffusion transfer process, that in an exposed light-sensitive silver salt layer of a photographic material a latent image is developed and an image is precipitated by diffusion transfer in an image receiving layer will. The invention also relates to a photographic material for carrying out the method with a Layer support and at least one silver salt layer applied thereon, an image receiving layer and one in one Containers arranged, optionally viscous, a silver halide solvent containing developer or activator solution for the development or activation of the exposed silver salt layer.

It is known, for example, from U.S. Patents 2,698,237; 2,647,056; 3 108 001 and 3 345 166 to produce photographic images by diffusion transfer. The main advantage of one

1 0 98 i

Diffusion transfer method is that positive images can be obtained in one process step. To the Carrying out the diffusion transfer process is a photographic recording material having a photosensitive Layer, especially a photosensitive emulsion layer and an image receiving layer or precipitating layer, which are adjacent is arranged to the photosensitive layer or with this is brought into contact. After exposure of the photosensitive photographic layer, a working solution, in particular developer solution between the exposed photographic layer and the image receiving layer or Brought precipitation layer. Contains the working or developer solution Usually a silver halide solvent, for example sodium thiosulphate, which dissolves the unexposed silver salts, usually silver halides, to form a silver complex, which then enters the image-receiving layer or ^ * Precipitation layer diffuses, in which development nuclei or image-precipitating agents the silver from the silver complex imagewise fail. The development nuclei or precipitating agents can be brought into contact in the image receiving layer before be present with the complex-bound silver. The development germs however, they can also be generated "in situ".

The methods used to carry out the diffusion transfer process

Is applicable

Applied working solutions usually fold a developer compound and are usually used in the form of viscous liquids that are in the form of a liquid layer between the photographic photosensitive layer and the image-receiving layer to be spread out.

To those for performing the diffusion transfer process Appropriate developer compounds are subject to high requirements and it has been shown that only relatively few of the

1 0 9 8 1 5/1? 2 1

known developer compounds, which are necessary to carry out the all-. Commonly used silver halide development processes suitable **, sufficient results for diffusion transfer processes deliver. A silver halide developer compound which leads to relatively unsatisfactory results in diffusion transfer processes consists of a 2,4-diaminophenol, e.g. 2,4-diaminophenol hydrochloride, also known as amidol. However, although such developer compounds a produce a positive image, they have serious disadvantages, in particular because they are quick to oxidize subject. The oxidation products resulting from the oxidation in turn cause unsightly discolouration of the positive ones Image copy.

Surprisingly, it has been shown that developer compounds, which can be successfully used to develop conventional silver halide emulsion layers in conventional photographic development processes do not result in discoloration reduction in the diffusion transfer process. These The fact emerges, for example, from Examples 2, 3 and 4 which follow later, in which it is shown that 6-methoxy-2,4-diaminophenol, hydroquinone and t-butylhydroquinone lead to discoloration of the positive copy.

There is thus a need for developer compounds which, without interfering with the sensitometric properties and the development process in the diffusion transfer process, lead to positive images which are not or only slightly discolored by the oxidation products of the developer compounds.

The object of the invention is “to provide a photographic diffusion transfer process which enables the production of positive images which are not or at most only slightly

109 81 6 / 1.72

by those used to develop the recording material Developer compounds become discolored.

The invention is based on the surprising finding that Anhydrodihydroreductene silver halide developing agent compounds are excellent for carrying out the diffusion transfer photographic process.

The subject matter of the invention is therefore based on a photographic diffusion transfer process in which a latent image is developed and exposed in the light-sensitive silver salt layer of a photographic recording material which is exposed at the same time an image is precipitated by diffusion transfer in an image receiving layer, and is characterized in that an anhydrodihydroreductone silver halide developing agent is used to develop the latent image.

The subject matter of the invention also relates to a photographic material for carrying out the method with a layer support and at least one silver salt layer applied thereon, an image receiving layer and one in a container arranged, optionally viscous, developer or activator solution containing a silver halide solvent for the Development or activation of the exposed silver salt layer and is characterized in that the material in at least a layer and / or the developing solution contains an anhydroreductone silver halide developing agent.

The invention provides that positive images in the diffusion transfer photographic process without impairment of the sensitometric properties without

by the silver halide developer compounds used caused discoloration or at most minimal discoloration can be obtained. Preferably for To carry out the process, photographic materials having at least one silver halide emulsion layer are used.

Advantageously, the invention can be used

the anhydrodihydroreductone silver halide developing agent compounds combine with other known silver halide developing agents, in particular with pyrimidine silver halide developing agents as well as aminomethylhydroquinone developer compounds, Cinnamic acid developer compounds and coumarin developer compounds or corresponding developer precursor compounds.

Surprisingly, it has been shown that the invention used anhydrodihydroreductone silver halide developer compounds as part of a diffusion transfer process offer significant advantages over reductone developing agents because of their unexpected properties. Thus, when they are used, desirable sensitometric properties can be achieved at concentrations that are considerable are below those obtained using reductone silver halide developer compounds are generally required.

To carry out the method of the invention, the most varied Anhydrodihydroreductone silver halide developing compounds can be used. Typical, for the implementation of the Anhydrodihydroreductone silver halide developer compounds particularly suitable for the process of the invention, which not only lead to a reduction in discoloration or even elimination

10 9 816/1221

discoloration and also excellent developing activity have and neither the maximum density nor the minimum density, nor the photographic speed and the Qamma values and other sensitometric properties of the Anhydrodihydroaminoreductone silver halide developing agent compounds adversely affect photographic material.

Advantageously, anhydrodihydroreductone silver halide developer compounds are used in carrying out the process of the invention the following structural formula is used:

here mean:

in each case hydrogen atoms or alkyl radicals, preferably with 1 to 5 carbon atoms, e.g. methyl, ethyl, propyl or pentyl radicals or together the atoms that are required to complete a heterocyclic nucleus, as can be seen from the dashed curve.

If R ₁ and R- together form a heterocyclic nucleus containing a nitrogen atom, this nucleus preferably has

r L £ ν 1.1 ^ cc *. ν c Ji for example. 5 to 6 carbon atoms in the nucleus and can also / a second

109815/1221

Contain nitrogen atoms * or an oxygen atom. This means that R ₁ and R _{2 can form,} for example, a morpholino, piperazino, pyrrolidino or piperidino nucleus.

Typical advantageous anhydrodihydroreductone silver halide developer compounds suitable for carrying out the process of the invention are, for example:

Anhydrodihydrodimethylaminohexose reductone, Anhydrodihydrodiallylaminohexose reductone, Anhydrodihydrodi-n-butylaminohexose reductone, Anhydrodihydrodi-n-hexylaminohexose reductone, Anhydrodihydromorpholinohexose reductone, Anhydrodihydropiperazino-di-hexose reducton), Anhydrodihydropyrrolidinohexose reductone, Anhydrodihydropiperidinohexose reductone, Anhydrodihydrodimethylmorpholinohexose reductone Anhydrodihydromethylpiperidinohexose reductone and Anhydrodihydro-N-benzyl-N-methylaminohexose reductone.

The anhydrodihydroreductone silver halide developer compounds used in accordance with the invention can be used more advantageously Manner from the corresponding anhydrohexose reductone compounds, which in turn can be obtained from the corresponding aminohexose reductones.

A typical process for making aminohexose reductones and anhydroaminohexose reductones are known from U.S. Patent No. 2,936,308. Such compounds can be advantageously prepared from Zuckeγ ^ in particular D-glucose, although other reducing sugars, e.g. D-galactose, D-fructos8f? E-sorbose, are also suitable for their production.

10 9015/122

A typical process for the preparation of the aminohexose reductones used as starting compounds is that in a practically anhydrous reaction medium a reducing hexose sugar and an aliphatic or cyclic secondary amine in the presence of an acidic one which forms a reductone Catalyst, e.g. phosphoric acid, boric acid, acetic acid or succinic acid. In the formation of the aminohexose reductone, 3 moles of water are removed.

The desired anhydroaminohexose reductones can then be obtained by heating the hydrochloride salts of the aminohexose reductones in the presence of a strong acid such as sulfuric acid, acetic anhydride, zinc chloride and the like to remove a Make more moles of water. The desired Dihydroanhydrohexosereductone can in turn from those described Anhydroaminoreductones can be prepared by hydrogenation in the presence of a suitable catalyst, e.g. Raney nickel.

The preparation of anhydrodihydropiperidinohexose reductone is typical of the preparation of those used in the present invention Anhydrodihydroreductone silver halide developing compounds. To produce the anhydrodihydropiperidinohexose reductone, for example, one mole of anhydrous D-glucose and 1.3 moles Piperidine stirred together in absolute ether under nitrogen for 15 minutes. The mixture obtained is then on a Steam bath stirred until the solution becomes homogeneous. A solution of glacial acetic acid in absolute ethanol is then added dropwise to the solution. The resulting solution is then taken under Stir and reflux under nitrogen for 12 hours. It is then cooled, whereupon the adbohc excreted Crystals are filtered off, washed and e.g. uakristallisiert from ethanol. The resulting piperidinohexose reductone is then

109815/1? 21

in a butanolic solution of anhydrous hydrogen chloride dehydrated, whereby anhydrodihydropiperidinohexosereductone is obtained as an intermediate product. This compound is then made into ethanol in the presence of a suitable catalyst, e.g. Raney nickel hydrogenated to form the desired anhydrodihydropiperidinohexose reductone. The resulting reaction product can optionally by recrystallization from a suitable solvent, e.g. ethanol can be cleaned.

The anhydrodihydroreductone silver halide developer compounds described can be in the form of the free base or else in the form of an acid salt, e.g. as a hydrochloride, sulfate or The like. Can be used. This means that the anhydrodihydroreductone silver halide developing compounds used in the present invention can be used in the form of their salts or in their non-salt form.

According to the invention, the anhydrodihydroreductone silver halide developer compounds described can be placed in various ways within the scope of the diffusion transfer process. So can they are used, for example, in one or more layers of the photographic recording material used to carry out the process or in a working or developing solution. The most favorable position of the developing agent in the individual case depends on the properties of the desired image, the process conditions and the like. Ώ. The anhydrodihydroreductone silver halide developer compounds described can thus, for example, when used in a working solution, can be used in an aqueous alkaline developer solution or but they can include, for example, one or more layers of photographic recording material, e.g., photographic Silver halide emulsion layers, a layer between the

109815/1221

Support and a silver halide emulsion layer and / or an overcoat layer can be used.

In detail, the process of the invention can be carried out by customary known methods and using customary photographic materials, as described, for example, in U.S. Patents 2,352,014; 2,452,181 and 3,337,342 are known.

The method of the invention can thus also be a so-called highly sensitive one Diffusion transfer processes such as is known from US Pat. No. 3,326,683 or a diffusion transfer process such as that disclosed in U.S. Patents 2,857,274; 3,020,155; 2,584,030 or 2,923,623. In these patents, moreover, to carry out the diffusion transfer process suitable photographic materials have been described of construction which is also suitable for practicing the method of the invention Applies. The photographic products known from the last-mentioned USA patents consist of one Combination of (a) a photographic element with a photographic silver halide layer; (b) a working solution with a silver halide solution agent, more typically and advantageously Arranged in a frangible container and (c) an image receiving layer.

Accordingly, in one embodiment of the invention, the invention relates to a photographic material consisting of the combination of (a) a photographic element with a photographic silver halide layer, (b) a working solution with a silver halide solvent and (c) an image-receiving layer, the photographic material of the invention thereby

109815/1221

is characterized as having an anhydrodihydroreductone silver halide developing compound. The anhydrodihydroreductone silver halide developing agent can, as already set out, be accommodated in different places, e.g. in photographic recording material, in working or Developer solution and / or in the image-receiving layer or in a layer * which is adjacent to the light-sensitive layer or the image-receiving layer.

It has been found that the developer compounds used according to the invention are suitable for developing a wide variety of photographic emulsions. For example, the developer compounds are suitable for developing X-ray emulsions or other non-spectrally sensitized emulsions and / or for developing emulsions which spectral sensitizing dyes such as those disclosed in U.S. Patents 2,526,632 and 2,503 are known. Typical spectral sensitizers used to sensitize the emulsion layers are, for example, cyanines, merocyanines, complex trinuclear cyanines, complex trinuclear merocyanines, styryls and hemicyanines.

The silver salt layer of the photographic material used for carrying out the process of the invention can contain a wide variety of silver halides as silver salts, e.g. Silver bromide, silver chloride, as well as mixed halides, e.g. silver broaoiodide, silver chloroiodide and the like. This means that the silver salt can consist of any of the conventionally known silver salts used to carry out photographic silver salt diffusion transfer processes.

109815/1? 21

The support of the material used to carry out the method of the invention can be any of the conventionally known supports used to carry out the diffusion transfer process. For example, the support can consist of a cellulose nitrate film, a Cellulose esters, polyvinyl acetal, polystyrene or a polyester, e.g. polyethylene terephthalate, and also of paper or from paper coated with a plastic, for example from a paper coated with an α-olefin polymer, in particular with an α-01efin coated paper with 2 to 4 carbon atoms, e.g. a paper made with polyethylene, polypropylene or an ethylene-butene copolymer is coated. Finally, the layer support can also consist of glass or a metal. Optionally, the support or on these applied layers, e.g. paper backing, contain fluorescent optical brighteners, for example those on Stilbene, benzothiazole, becoxazole or coumarin base.

The natural and synthetic materials customarily used for the production of photographic materials can be used for the production of the recording materials and image-receiving layers Binding agents can be used, e.g. gelatine, colloidal albumin, water-soluble vinyl polymers, M * i «xxNXiix £ fti) ca * KkftX * jlft $ Cellulose derivatives, acrylamide polymers, polyvinylpyrrolidone and the like. Finally, mixtures of such binders can also be used. Such binders can also contain other dispersed polyerized vinyl compounds. Such compounds are known, for example, from US Patents 3,142,568; 3,193,383; 3,062,674 and 3,220,844 are known. to they include, for example, water-insoluble polymers of

109815/1221

Alkyl acrylates and alkyl methacrylates, acrylic acid, sulfoalkyl acrylates and sulfoalkyl methacrylates, and the like. Optionally For example, the photographic materials used to carry out the process of the invention can also have so-called stripping layers and / or antistatic layers, i.e. conductive layers.

The photographic emulsion layers one for implementation Materials useful in the method of the invention may further include conventional sensitivity increasing compounds, e.g. have quaternary ammonium compounds, polyethylene glycols or thioethers. If necessary, advantageous effects can be achieved can also be obtained when the described sensitivity-increasing compounds are added to the working solutions or developing solutions instead of being incorporated into the photographic emulsion layer.

For the production of a recording material to carry out Silver halide photographic emulsions used in the process of the invention can be chemically prepared in a conventional manner sensitized, for example by digesting with naturally active gelatins or various sulfur, Selenium, tellurium or noble metal sensitizers and / or reduction sensitizers. Combinations of these sensitizers can also be used, as is known, for example, from U.S. Patents 3,297,446 and 3,408,196.

In the context of the invention, the developer compounds described can be used in combination with the most varied of customary known additives which are used for developing and working up photographic materials, in particular

109815/1221

sochen used in diffusion transfer photographic processes be used. These include, for example, hardeners such as those from British patent specification 974 317 are known, buffer compounds to maintain the desired development activity and / or the pH value, coating aids, Plasticizers and stabilizers such as sodium sulfite.

The described developer compounds used according to the invention can finally also be used in an advantageous manner in multilayer, one element materials within the framework of Diffusion transfer processes can be used which remove the undeveloped silver halide of the non-image areas of a Negative for the formation of a positive through the physical development of this silver in a nucleus or nucleus containing adjacent, image receiving layer, whereupon the top layer is removed by scraping or rubbing, washing or the like will. Processes of this type are known from US Pat. No. 3,020,155, for example.

10 9 8 15/1221

Good results, which are improved in particular by an Further, expressing tone and desirable contrast are obtained using photographic materials or elements of the type described when using them a so-called outer development belt, which contains the described developer compounds in combination with a silver halide solvent and other working, developing or coating components, the latter In a binder or carrier on a suitable layer carrier, developing or working tapes are arranged Type are, for example, from US Pat. No. 3,179,517 known.

109815/1771

The developer compounds described, used according to the invention, can finally also be used in one or more layers of a photographic material which is used for recording determined by color images. For example, the developer compounds used according to the invention can can be incorporated into one or more layers of photographic material which is photographic as opposed to has a layer sensitive to the blue region of the spectrum, and a photographic layer which is sensitive to the green region of the spectrum Spectrum sensitive layer and finally a photographic layer sensitive to the red region of the spectrum Layer. The layers which are sensitive to the blue, green and red regions of the spectrum can furthermore contain conventional sensitizing dyes. Photographic Materials which are intended for recording color images and in which the developing agents used in the present invention can be used are described, for example, in the book by Mees, "The Theory of the Photographic Process "3rd Edition, 1966, pages 382-396.

As already stated, the developer compounds used according to the invention can also be used in photographic materials which contain development nuclei or silver precipitates Have cores, e.g., an image receiving layer. As already stated, they can also be used in photographic materials or Elements and / or working or developing solutions intended for use with these image receiving layers.

The image-receiving layer used for carrying out the method of the invention can be any of those conventionally known

109815/17 2

Physical development nuclei common to diffusion transfer systems or contain chemical precipitants, e.g. (a) heavy metals in colloidal form and salts of these metals; (b) salts of amines, which form silver salts and / or (c) non-diffusing polymeric substances with functional groups, that can combine with silver amines.

Development nuclei or agents which precipitate silver images are therefore, for example, suitable for the production of an image-receiving layer Metal sulfides, selenides, polysulfides, polyselenides, thiourea and its derivatives, stannous halides, silver, gold, Platinum, palladium and mercury, colloidal sulfur, aminoquanidine sulfate, Aminoguanidine carbonate, arsenic oxide, sodium stannite, hydrazines, xanthates and corresponding compounds, such as, for example from US Pat. No. 3,020,155. Finally, for example, non-diffusing polymers can also be used Silver precipitating substances or development nuclei such as polyvinyl mercaptoacetate can be used. The development seeds or silver precipitating agents can be used in a wide variety of concentrations. However, the concentrations must be at least large enough to ensure the development of a positive image and sufficient distance of undeveloped silver salt from the photosensitive to developing layer takes place.

It has proven advantageous, for example, to use the developer compound at a concentration of about / "320 mg per

2
Use 0.0929 m (1 square foot) of the layer containing the development nuclei or precipitants.

The developer compounds used according to the invention can also be used in combination with the customary known silver

/ "3 to 10 9 815/1221

halogenide developer compounds are used.

Suitable silver halide developer compounds which together with the anhydrodihydroreductone silver halide developer compounds described can be used are, for example, polyhydroxybenzenes, e.g. hydroquinone developer compounds, e.g. hydroquinone, hydroquinones substituted by alkyl radicals, e.g. t-butyl hydroquinone, methyl hydroquinone and 2,5-dimethyl hydroquinone, Catechol and pyrogallol, aminomethylhydroquinones, Ilydroquinones substituted with chlorine, e.g. chlorohydroquinone and dichlorohydroquinone, Ilydroquinones substituted by alkoxy radicals, e.g. methoxyhydroquinone and ethoxyhydroquinone, aminophenol developer compounds, e.g. 2,4-diaminophenols and methylaminophenols, pyrimidine destacking compounds, ascorbic acid developer compounds, e.g. ascorbic acid and ascorbic acid ketals "as they are known, for example, from" US Pat. No. 3,337,342. Further can with the developer compounds used according to the invention, for example, developer compounds such as hydroxylamine or 3-pyrazolidone developing compounds, e.g., 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone can be used, including those compounds as disclosed in British Patent 930 5 72 are known. Furthermore, with the developer compounds used according to the invention for example acyl derivatives of t-aminophenol are used, as known, for example, from British patent specification 1,045,303.

109815/1221

The developer compounds used according to the invention can thus, for example, be used together in combination with the following compounds:

1-phenyl-3-pyrazolidone

Hydroquinone Methy! Hydroquinone

2,5-dimethylhydroquinone

2,6-dimethylhydroquinone

trButy! hydroquinone

3,6-dihydroxybenzonorbornane

2,4-diamino-6-methylphenyl dihydrochloride 4-phenylcatechol

t-buty! pyrocatechol

2,4-diaminophenol dihydrochloride

Ascorbic acid N-methyl-p-aminophenol sulfate N, N ¹ -ethylene diCoxymethyl / pyridinium perchlorate and.

7,14-diazo-6-1S-dioxoeicosane-1,21-bis (pyridinium perchlorate).

The compounds described can, for example, be incorporated into a photographic material of the type used in a diffusion transfer process which, after exposure, can then be developed with a developing solution containing one of the described developing agents used in accordance with the invention. One or more of the described combinations of compounds can des further in that for carrying out the method of the invention used photographic material and / or in the work station used to develop the material

10 9 8 15/1221

solution, e.g. the developer solution. For example, a photographic material can be used which contains a 3-pyrazolidone developing agent and / or a 2,4-diaminophenol developing agent and / or a polyhydroxybenzene developing agent and / or other additives described. The material can be developed using a working or developing solution that is an anhydrodihydroreductone developer compound of the type used according to the invention.

As already stated, the anhydrodihydroreductone developer compounds used according to the invention can, for example in a silver salt photographic emulsion layer commonly used for performing a diffusion transfer process is used, used and / or in a working or developing solution such as that used to carry out the Diffusion transfer process is needed. A typical working or developer solution, such as those used to carry out a Diffusion transfer process is required, for example known from US patent specification 3,120,795.

Accordingly, the anhydrodihydroreductone developing agents used in the present invention be contained, for example, in a liquid photographic working or developer solution, which contains: (A) a silver halide solvent; and (B) a silver halide developing agent, wherein the silver halide developing agent according to the invention at least in part from an anhydrodihydroaminoreductone silver halide developer compound consists.

Viscous developer solutions can thus advantageously be used to carry out the method of the invention

15/1791

whose main components consist of:

1. a silver halide solvent;

2. an alkaline development activator and

3. An anhydrodihydroaminoreductone-silver-ethogenide developer compound.

Preferably, such a developing solution is used for development and transferring an image to an image receiving layer, which contains palladium development nuclei dispersed in a conventional polymeric binder.

Those used to carry out the method of the invention As already stated, developer or working solutions are advantageously viscous developer or working solutions their viscosity can be very different. Usually solutions with viscosities from about 20 to about 100,000 centipoise used. To prepare the solutions, customary known thickeners can be used, such as they are used, for example, for the production of the customary known viscous monobaths. These include, for example the thickeners known from U.S. Patent 3,120,79S, e.g., hydroxyethyl cellulose and carboxymethyl cellulose.

Typical suitable viscous monobaths in which the anhydrodihydroreductone silver halide developer compounds described can be used are known , for example, from the "Monobath Manual" by Grant M. Ilaist (1966) and US Pat. No. 3,392,019 .

To carry out the process of the invention, a wide variety of customary known silver halide solutions can also be used.

109815 / 1.221

2009Π78

medium can be used. Sodium thiosulfate is preferably used as the silver halide solvent, although also A wide variety of other organic silver halide complex-forming compounds can be used, as described, for example, by Haist and co-workers in the journal "Photographic Science and Engineering ", Volume 5, page 198 (1961), French Patent 1,312,687 and Belgian Patent 606 559.

The method of the invention is particularly suitable for the production of black and white images, i.e. the method of the invention is typically a so-called black and white silver diffusion transfer process.

The method of the invention is carried out at a pH in which the anhydrodihydroreductone silver halide developer compounds described are activated. The activation pH is usually about 10 to about 14, with particularly good results being obtained when the pH is is above about 12. If the pH of the system drops to less than about 8, e.g. between about 2 and 8, the Development activity interrupted. The optimum pH of a particular diffusion transfer system is influenced by the particular photographic material used, and also by the quality of the image desired, the additive used in the working or developing solution, the composition of the Emulsion layer and the image receiving layer, working conditions and the like.

Any development activator can be used to perform the process can be used, which adjusts the desired pH. Typical

109815/1221

See development activators suitable for practicing the method of the invention are, for example, alkali metal hydroxides, e.g., sodium hydroxide, potassium hydroxide and Lithium hydroxide, as well as organic development activators, especially amines, e.g. 2-aminoethanol, 2-methylaminoethanol, 2-dimethylaminoethanol, 2-ethylaminoethanol, 2-diethylaminoethanol, 2,2'-diiminodiethanol, and 5-diethylamino-2-pentanol.

As part of the diffusion transfer process of the invention Thus, a photographic material having a photographic silver salt layer, particularly a silver halide emulsion layer, can be used to form a latent image in the Layer are exposed, whereupon the latent image obtained is developed with a developer solution which has a pH from about 12 to about 14 and which contains an anhydrodihydroreductone silver halide developing compound, wherein or whereupon the undeveloped silver salts of the light-sensitive silver salt photographic layer are brought into contact with a silver halide solvent, thereby imagewise Distribution of a silver complex in the unexposed areas of the photographic silver salt layer takes place. At least part of the silver complex will project onto an image-receiving layer, which is coated with the photographic silver complex • is in contact, producing a visible image in the image-receiving layer due to the presence of development nuclei will.

The process conditions such as the development time and the like. can depend on various factors, e.g. the quality of the image desired, the particular composition of the photographic material used, the workflow, the Composition of the system and the image receiving layer.

10 9 8 15/1221

2009Π78

Typically, the process is carried out under normal atmospheric conditions, being carried out within about 60 seconds, for example within 10 seconds. The process temperatures are typically around 20 to around 30 ° C. However, if necessary, higher temperatures can also be used, for example temperatures up to about 50 ^° C.

The recording materials used for carrying out the process of the invention can advantageously be image-receiving layers or image receiving materials and / or developer or working solutions also contain so-called toners. Typical toner or Toning agents suitable for practicing the method of the invention are, for example, polyvalent inorganic ones Salts, such as those disclosed in US Pat. No. 2,698,236, silica, the use thereof, for example, from US Pat 2,698,237 is known and heterocyclic mercaptans, e.g., mercaptoazoles, e.g., mercaptodiazoles, mercaptotriazoles and Mereaptotetrazole.

The concentration of the developer compounds used according to the invention can be very different and depends somewhat on the specific photographic and physical variables of each the system used, e.g. the placement of the developing agent in the system, the recording material used, the composition of the developing solution and the quality of the desired image, the process conditions and the like. The im In individual cases, the most favorable concentrations also depend on the additives present in the individual case in the photographic recording.

1 0 9 8 1 5/1? 2 1

2009073

Drawing material to be developed and / or the addition of the developer or working solution »*.

If one of the described developer compounds used according to the invention is used in the photographic material, in this case, concentrations of from about 0.01 to about 5 moles of developing agent per mole of silver halide are preferred of the photographic material used. In contrast, if one of the developer compounds used according to the invention is used in a working or developer solution, then so the concentration of the developer compound in the working or developer solution depends on the fact that the total concentration of the developer compounds in the system is from about 0.01 to about 10, preferably 1 to about 5 percent by weight, based on the weight the entire developer mass or developer mixture; / ~

Often, it has proved advantageous to carry out the process in the presence of an antifoggant, £> d in the photographic material itself or the developer working solution or can be accommodated. Advantageous antifoggants consist of organic antifoggants, for example benzotriazole, benzimidazoles, 2-mercaptobenzimidazole, nitroidazole and mercaptotetrazole antifoggants. However, the developer solutions or working solutions can also contain inorganic fogging agents, for example potassium bromide, potassium iodide and / or sodium bromide. The concentration of the antifoggants both in the developer solutions and in the photographic material itself can vary widely, depending on the quality of the image desired, the components present, the process conditions and the like. It has been found to be useful if the developer solution contains less than about 2% by weight of antifoggant, preferably about 0.01 to 2% by weight of anti-fogging agent.

/ i.e. about 0.01 to about 10 weight percent solutions can be used.

109815/1221

added to the total weight of the developer solution.

According to the invention, particularly advantageous results are obtained when the anhydrodihydroreductone silver halide developer compounds used according to the invention together with other silver halide developing agents such as hydroxycinnamic acid silver halide developing compounds and / or so-called lactone silver halide precursor developing compounds and / or pyrimidine silver halide developing compounds and / or aminomethyl polyhydroxybenzene silver halide developing compounds.

According to the invention, in addition to the anhydodihydroreductone silver halide developer compounds used, a or several of the developer compounds described are placed in the most varied of ways in the diffusion transfer system. For example, one or more of the described Developer compounds are used in one or more layers of the photographic recording material used for carrying out the method of the invention and / or in the developer solution and / or in the image receiving layer used to carry out the method of the invention. So is it is possible, for example, that one or more of the developer compounds described are used in the developer solution e.g. an aqueous alkaline developer solution and / or one or more of the developer compounds described are incorporated into a layer of the photographic material, e.g., a silver salt emulsion layer, preferably a silver halide emulsion layer, an overcoat layer or a layer between the emulsion layer and the support and / or another layer, that of the silver salt layer

815/1221

is neighboring that is to be developed.

In a particularly advantageous manner, pyrimidine-silver halide developer compounds can be used for carrying out the process of the invention in combination with the anhydrodihydroreductone silver halide developer compounds described be used.

Particularly suitable ones for carrying out the method of the invention Pyrimidine silver halide developer compounds are, for example:

4-amino-5,6-dihydroxy-2-methylpyrimidine, 2,5-dihydroxy-4,6-dimethylpyrimidine, 2-amino-4,5-dihydroxypyrimidine, 2-piperidino-4,5-dihydroxy-6-methylpyrimidine, 2,4-diamino-5-hydroxy-6-methylpyrimidine, 2,4-diamino-5-hydroxypyrimidine, 2,5-diamino-4,6-dihydroxypyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2, 4,6-trihydroxy-5-aminopyrimidine, 2,4,5,6-tetrahydroxypyrimidine, 2-methyl-4-amino-5,6-dihydroxypyrimidine, 2-amino-4,5-dihydroxy-6-methylpyrimidine, 2, 4,5-trihydroxy-6-methylpyrimidine 2 , 4,5-triaminopyrimidine.

109815/172

Pyrimidine silver halide developing compounds are inherent known, e.g. from the journal "Photographic Science and Engineering", No. * 3, May-June issue, 1959, pages 135 to 139.

The described pyrimidh silver halide developer compounds can typically be used in the form of an acid salt, e.g., in the form of a hydrochloride, chloride, sulfate, or the like. But they can also be in their non-salt form be used.

A wide variety of cinnamic acid silver halide developing compounds together with the anhydrodihydroreductone silver halide developing compounds described are also suitable for carrying out the process of the invention.

Typical advantageous cinnamic acid silver halide developing compounds suitable for carrying out the process of the invention are, for example:

3-4-dimethyl-2,5-dihydroxycinnamic acid, 4-methyl-2,5-dihydroxycinnamic acid, 6-bromo-4-methyl-2,5-dihydroxycinnamic acid, 2-hydroxy-5-aminocinnamic acid,

ß-methyl-2-hydroxy-4-methoxy-5-aminocinnamic acid, 3-4-dimethyl-2-hydroxy-5-aminocinnamic acid, ß-methyl-2,5-dihydroxy-4-methoxycinnamic acid, 2-hydroxy-S-methylaminocinnamic acid, 4-t.-butyl-2,5-dihydroxycinnamic acid, 2,5-dihydroxycinnamic acid,

2,5-dihydroxy-3,470-trimethylcinnamic acid and 2,3-dihydroxycinnainic acid.

1 Ü 9 8 1 S / ι? ? 1

The use of cinnamic acid silver halide developing compounds in the context of diffusion transfer processes is described in more detail in the US patent application with Ser.No. 764 301 as well as in the German patent application with the file number P 19 49 403.

Typical cinnamic acid silver halide developing agents useful in practicing the process of the invention are derived of corresponding hydroxycoumarin and / or aminocoumarin developer precursor compounds away. Suitable aminocoumarin and / or hydroxycoumarin developer precursor compounds described in the context of of the invention can be used, for example:

8-hydroxycoumarin,

6-hydroxy-5,7-dimethoxycoumarin, 6-hydroxy-4,7-dimethylcoumarin, 6-hydroxy-5,7-diethoxy-4-methylcoumarin, 6-hydroxycoumarin,

8-hydroxy-4-methylcoumarin,

6-hydroxy-4-methylcoumarin,

7- (benzyloxy) -6-hydroxycoumarin, o-hydroxycoumarin-S-sulfonic acid, 6-hydroxycoumarin-S-sulfinic acid, 4,6-dihydroxycoumarin,

8-aminocoumarin,

6-aminocoumarin,

6-amino-5,7-dimethoxycoumarin,

8-amino-4-methylcoumarin,

6-amino-5,6-diethoxy-4-methylcoumarin, o-amino-e-hydroxycoumarin,

o-hydroxy-e-aminocoumarin,

6,7-dihydroxy-4-methyl-3,4-dihydrocoumarin and 7,8-dihydroxy-4-methyl-3,4-dihydrocoumarin.

109815/1221

Furthermore, a wide variety of aminoalkylhydroquinone silver halide developer compounds can be used according to the invention can be used together with the anhydrodihydroreductone silver halide developing agent compounds described.

Typical aminomethylhydroquinone developer compounds suitable for carrying out the process of the invention are, for example:

2-morpholinomethy! Hydroquinone, 2-piperidinomethyl! Hydroquinone, 2-pyrrolidinomethylhydroquinone, 2-methyl-5- (4-methylpiperazinomethyl) hydroquinone, 2-pyrimidinomethylhydroquinone, 2,5-bis (dimorpholinomethyl) hydroquinone, 2,5-bis (dipiperazinomethyl) hydroquinone, 2,5-bis (dipiperidinomethyl) hydroquinone, 2-methyl-S-morpholinomethylhydroquinone, 2-methyl-5-pyrrolidinoraethy! Hydroquinone, 2-methyl-5-piperidinomethyl! Hydroquinone, 2-methoxy-5-morpholinomethy / hydroquinone 2-methyl-5-bis (hydroxyethyl) aminomethylhydroquinone and 2-i.-Butyl-5-morpholinomethyl / hydroquinone.

These compounds can typically be in the form of their acid salts, e.g. in the form of their QAorides, sulfates or hydrochlorides or alkali metal salts, e.g. their sodium or Potassium salts can be used.

109815/1221

The following examples are intended to illustrate the invention in more detail.

example 1

This example illustrates the use of an anhydrodihydroreductone silver halide developing agent in the frame a diffusion transfer method according to the invention.

First, a developing solution was prepared by mixing the following ingredients together.

Sodium sulfite 60.0 g Sodium thiosulfate, pentahydrate 40.0 g Sodium iodide 1.5 g Sodium Hydroxide 64, og

Hydroxyethyl cellulose (trade name Natrasol 25OH, manufacturer Hercules Powder Company USA) 25.0 g

Anhydrodihydropiperidino

hexose reducton 5.0 g

made up to 1 liter with water

The developer solution obtained consisted of a viscous one Liquid.

At the same time, a photographic recording material was produced in which on a layer support made of paper with a Electron-irradiated polyethylene layer was applied with a gelatin solution which contained Z-methyl-S-morpholinomethylhydroquinone as the silver halide developer compound. the Gelatin solution was applied to the substrate in this way.

2 bear that on a carrier area of 0.0929 m 240 mg of gelatin and 40 rag of developer compound were allotted. A coarse-grained gelatin-silver bromoiodide emulsion layer with 5 mole percent iodide was then applied over this layer in such a way that 125 mg of silver and 320 mg of gelatin accounted for ^{a support area of 0.0929 m 2.}

Furthermore, an image-receiving sheet was produced by placing a on a water-resistant paper support Dispersion of palladium development nuclei in a polymeric binder was applied.

The photographic recording material produced in the manner described was then exposed sensitometrically. The developer solution prepared in the manner described was then distributed between the recording material and the image-receiving sheet, whereupon the sandwich thus obtained was passed through the gap formed by two rollers with compression. After 20 seconds it became recording material and image-receiving sheet separated from one another, whereupon the image formed in the image-receiving layer is confirmed to be present has been tested for oxidation discoloration. The procedure described was repeated except that a developing solution was used which did not contain anhydrodihydropiperidinohexose reductone.

This second experiment served as a comparative experiment.

A value of 100 was assigned to the relative sensitivity of the comparison image on the image-receiving layer. the maximum density was 1.15. The manufactured according to the invention Image, i.e. the image created using the anhydrodihydro

109815/1

piperidinohexose reductons had a relative Sensitivity of 100 and a maximum density of 1.55. It follows that the use of the anhydrodihydropiperidinohexose reductone leads to an increase in the maximum density without reducing the photographic Sensitivity takes place.

In both cases, those produced in the image-receiving layers had No discoloration in the images.

Example 2 (comparative example).

First, a developer solution was prepared by mixing the following components together:

Potassium sulfite 50.0 g Sodium thiosulfate, pentahydrate 40.0 g Potassium iodide 1.6 g Potassium hydroxide 16.7 g Sodium hydroxide 17.5 g 6-methoxy-2,4-diaminophenol
dihydrochloride 30.0 g Hydroxyethyl cellulose (cf.
Example 1) , 30.0 g

The developing solution obtained consisted of a viscous liquid.

At the same time, a photographic material was prepared in which a coarse-grained gelatin-silver bromoiodide emulsion was coated on a film support.

Furthermore, an image-receiving sheet was prepared by applying a water-resistant paper support with a dispersion

109815/1221

was coated by palladium development nuclei in a polymeric binder.

The photographic recording material obtained was usually exposed sensitometrically. Thereupon the developing solution prepared in the manner described is spread between the recording material and the image-receiving layer of the image-receiving sheet, whereupon the resulting sandwich was pressed together by passing through the nip of two rollers. After 30 seconds, recording material and Image receiving sheet separated from each other, whereupon the image generated in the image receiving density checked for oxidation discoloration became.

It was found that the image produced had a strong yellow appearance orange discoloration.

It is clear from this example that a developing agent such as 2,4-diaminophenol leads to transfer images, that are heavily discolored.

Example 3 (comparative example)

The procedure described in Example 2 was repeated with except that this time hydroquinone was used in place of the 2,4-diaminophenol developing agent.

The positive image formed in the image receiving layer exhibited

strong yellow xxtesec orange discoloration. and

109815/1221

Example 4 (comparative example)

The procedure described in Example 2 was repeated with the exception that t-buty / hydroquinone was used in place of the 2,4-diaminophenol developing agent.

The image formed in the image receiving layer was strong yellow

xxfeor orange discoloration.

Example 5 (comparative example)

The procedure described in Example 1 was followed with the exception repeats that this time piperidinohexose reductone was used instead of the anhydrodihydropiperidinohexose reductone, wherein the concentration of the piperidinohexose reductone was 20.0 g per liter of developer solution.

The positive image obtained had a relative sensitivity from 80 to (compared to the comparison material from 100) and a maximum density of 1.55.

These results indicate that a higher concentration of piperidinohexose reductone is required to achieve the desired to obtain maximum density compared to the use of anhydrodihydropiperidinohexose reductone according to Example 1.

Examples 6 to 12

The procedure described in Example 1 was repeated except that the following anhydrodihydroreductone silver halide developing agent was used in place of the anhydrodihydro ■ piperidinohexose reductons were used.

109815/122

In all cases, corresponding results as described in Example 1 were obtained:

Example no. Developer compound

6 anhydrodihydrodimethylaminohexose

reductone

7 anhydrodihydrodiallylaminohexose

reductone

8 anhydrodihydrotli-n-butylaminohexose-

reductone

9 Anhydrodihydro-di-n-hexylaminohexose reductone

10 anhydrodihydromorpholinohexose

reductone

11 anhydrodihydropiperazino-di (hexose-

reductone)

12 anhydrodihydropyrrolidinohexose

reductone

As described, an advantageous concentration of the developer compound is about / * 320 mg per 0.0929 m of the layer, which contains the silver precipitating agent or the precipitation nuclei. On the other hand, as described, the concentration of developing agent can advantageously be about 2 g to about 50 g per liter of developer solution, for example 5 to 20 g per liter of solution.

The supports of the material used to carry out the method of the invention or those applied thereon Layers, typically paper supports, can optionally contain acids or acidic compounds, e.g., polymers Acids as described in U.S. Patents 2,584,030 and 3,415,644.

/ '3 to

10 9 8 15/1221

It has often proven advantageous to use an antioxidant in the photographic recording material to use. This is expediently incorporated into a layer which contains one of the developer compounds described contains. Typical antioxidants for this purpose are, for example, sodium formaldehyde bisulfite and those antioxidants described, for example, in the United States patents 3,212,895 and 3,418,132.

109815/1221

Claims (1)

Feb. 3, 1970 - 38 - Reg.Hr. 122 238 Claims Diffusion transfer photographic process in which in an exposed photosensitive silver salt layer of a photographic material, a latent image is developed and by diffusion transfer in a k image receiving layer an image is precipitated, characterized in that that an anhydrodihydro silver halide developing agent is used to develop the latent image used. A diffusion transfer photographic process according to claim 1, characterized in that an anhydrodihydroreductone silver halide developing agent is used the following structural formula is used: V γ-γΟΗ ^Κ 2 CH ₃ wherein R. and R ₂ each represent a hydrogen atom or an alkyl radical or together represent the atoms required to complete a heterocyclic ring. 3. Photographic diffusion transfer process according to claim 1 and 2, characterized in that anhydrodihydro- 109815/1221 -33- piperidinohexose reductone; Anhydrodihydromorpholinohexose reductone or anhydrodihydropyrimidinohexose reductone is used. 4. Diffusion transfer photographic process according to a of claims 1 to 3, characterized in that the anhydrodihydroreductone silver halide developer compound in the working solution used to develop the recording material. 5. Diffusion transfer photographic process according to a of claims 1 to 4, characterized in that the anhydrodihydroreductone silver halide developer compound used in conjunction with a second or auxiliary silver halide similar compound. 6. Photographic diffusion transfer process according to claim 5, characterized in that one as the second or Auxiliary silver halide developer compound a pyrimidine, Hydroxycinnamic acid or 3-pyrazolidone silver halide developing agent or a lecton silver halide precursor developing agent is used. 7. Photographic material for carrying out the method according to claims 1 to 6, with a layer support and at least one silver salt layer applied thereon, one Image-receiving layer and an optionally viscous developer or activator solution for the, which is arranged in a container and contains a silver halide solvent Development or activation of the exposed silver salt layer, characterized in that the material contains an anhydrodihydroreductone silver halide developer compound in at least one layer and / or the developer solution. 1098 1 S / 1.22!