DE2101408A1 - Photographisthes diffusion transfer process - Google Patents

Description

PATENT LAWYERS DR.-ING. WOLFF, H. BARTELS, DR. BRANDES, DR.-ING. HERO

25/81

8 MONKS 22 ... 25 ...... NpV .... 1970 THIERSCHSTRASSE 8 TELEPHONE: (08Π) 293297

Reg. No. 122 714

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

Photographic diffusion transfer process

109831/1432

210U08

The invention relates to a photographic diffusion transfer process, in which the photosensitive layer containing the light-sensitive layer in the development of an exposed silver salt of an undeveloped silver salt of a photographic material on an image-receiving layer containing a silver precipitating agent is transmitted.

The production of photographic images using a diffusion transfer process is known, for example from US Pat. No. 2,352,014. The usual diffusion transfer process is based on the fact that undeveloped silver salt, especially silver halide, of an exposed photographic Layer, in particular silver halide emulsion layer, in the form of a silver complex imagewise onto an image-receiving layer which contains a silver precipitating agent or silver precipitating nuclei. According to the well-known diffuse In particular, positive images can be generated in the image-receiving layer using ion transfer methods. The image receiving layer usually consists of a binding agent in which the silver precipitating agent, e.g. germs from nickel sulfide or a metal present in colloidal form.

There are several reasons why it is difficult to produce images which are satisfactory in all respects by means of a diffusion transfer process. For example, when carrying out the diffusion transfer process, brown or brown-tinged images are often obtained and / or images of only poor stability. There has therefore been no lack of attempts to improve the known diffusion transfer process with the aim of obtaining images of better quality. For example, it is known to add so-called toners or tinting agents to the developer solution used when carrying out the process, and to do special silver precipitants

109831 / U32

210U08

use or carry out the process in the presence of quaternary salts.

From the USA patent specification 2 699 393 it is known, for example, to improve the tint of the diffusion transfer process images, the process in the presence of phenyl mercaptotetrazoles, but the disadvantage of using such tetrazoles is that their stability the pictures obtained leaves something to be desired. Moreover, it has been shown that it is difficult to take pictures of a pleasing one To obtain tones, if certain binders are used for the production of the image-receiving layer, in which the Silver precipitant is dispersed. For example, protein colloids, e.g. gelatin, have proven to be special proven effective binders for dispersing silver precipitants. However, it has been shown that when using such proteinaceous colloids, e.g. gelatine, as a binder for the silver precipitating agent, e.g. silver precipitation nuclei, as in particular germs from colloidal silver, images are obtained which have a yellow to light brown hue are excellent.

The object of the invention is to provide a photographic diffusion transfer method to be indicated, neutral when it is carried out

109831 / U32

210U08

or black-tinted images can also be obtained if proteinaceous binders are used to produce the image-receiving layers, for example gelatin can be used.

The invention was based on the knowledge that the object can be achieved by the fact that the method in The presence of a 5-seleno-1,2,3,4-tetrazole.

The subject of the invention is thus based on a photographic one Diffusion transfer process in which the photosensitive Layer of a photographic material undeveloped silver salt on a silver precipitating agent containing image receiving layer is transferred from and is characterized in that the process in The presence of a 5-seleno-1,2,3,4-tetrazole.

The selenotetrazole used to carry out the process of the invention and producing the desired shade can be used in can be used in various ways. So it is possible to use the selenotetrazole to carry out the process To use developer or activator solution used and / or in the preferably of a silver halide emulsion layer existing silver salt layer of the recording material, provided that the selenotetrazole is currently the formation of the image is present in the image-receiving layer.

An image receiving layer is preferably used to carry out the method an alkali permeable organic colloid and a silver precipitating agent dispersed therein used, which additionally contains a 5-seleno-1,2,3,4-tetrazole. If the 5-seleno-1,2,3,4-tetrazole in the image receiving

109831 / U32

2Ί0Η08

layer used, so can optionally still further tetrazole in the used to carry out the process Developer or activator solution and / or the silver salt layer of the recording material can be used.

The concentration of 5-seleno-1,2,3,4-tetrazole in the image-receiving ^{layer is preferably about 0.01 mg to about 0.5 g per 0.0929 m 2 of} layer area. When using the selenotetrazole in the developer or activator solution, concentrations of 0.01 to about 1.0 g per liter of solution have proven to be particularly advantageous.

Variously substituted 5-seleno-1,2,3,4-tetrazoles are suitable for carrying out the process of the invention. For example, the selenotetrazoles can be substituted by aliphatic radicals, for example alkyl, aralkyl or Alkenyl radicals', or by aromatic or heterocyclic Leftovers. An advantageous 5-seleno-1,2,3,4-tetrazole, which by an aliphatic radical is substituted, for example, 1-allyl-5-seleno-1,2,3,4-tetrazole. An advantageous 5-seleno-1,2,3,4-tetrazole, which is substituted by an aromatic radical is, for example, i-phenyl-5-seleno-1,2,3,4-tetrazole.

Preferably, 5-seleno-1,2,3,4-tetrazoles of the following structural formula are used in carrying out the process of the invention used:

109831 / H32

210H08

where R means:

an alkyl radical having 1 to 10 carbon atoms, for example a methyl, ethyl, propyl or butyl radical, or a Aralkyl radical with 7 to 10 carbon atoms, e.g. a benzyl radical, or an alkenyl radical with 2 to 10 carbon atoms, e.g. an allyl radical, or an aryl radical, for example of the phenyl or naphthyl series having 6 to 10 carbon atoms e.g. a phenyl or tolyl radical.

The image-receiving layer can advantageously contain other known additives conventionally used for image-receiving layers, e.g. quaternary salts of polyvinyl compounds, an iodide, others known Toner or tinting agent or a silver salt, e.g. silver nitrate,

The image-receiving layer can also be coated with the photographic material form a unit or be arranged on a special layer support.

According to an advantageous embodiment of the invention, an express receiving material is used to carry out the method, which has been manufactured as follows:

First, silver precipitation nuclei consisting of a colloidal noble metal are usually stored in a proteinaceous binder, for example gelatin, containing a 5-seleno-1,2,3,4-tetrazole, for example 1-phenyl-5-seleno-1,2 , 3r 4-tetrazole, dispersed. A quaternary salt of a polyvinyl compound, for example poly (1-methyl-4-vinylpyridinium methyl sulfate) and / or an alkali iodide, for example potassium iodide, can also advantageously be present. The mixture obtained can then be applied in the usual way to a layer support, for example made of paper. After the layer has dried, the image-receiving material can be used to carry out a conventional diffusion transfer process. 109831/1432

210H08

According to a further advantageous embodiment of the invention, a material is used to carry out the method, which consists of a substrate, for example paper, and an image-receiving layer produced thereon in the manner described, after the image-receiving layer has dried, an uncured silver halide emulsion layer is applied to it . Emulsions known from US Pat. No. 3,020,155 are particularly suitable as uncured silver halide emulsion layers for application to the image-receiving layer. d

After the image-appropriate exposure of the recording material produced in the manner described, this can under Use of a silver halide developer solution containing a silver halide solvent, for example sodium thiosulfate, contains, to be developed. The undeveloped silver halide is complexed by the thiosulfate, whereupon the complex diffuses into the image-receiving layer disposed below the silver halide emulsion layer, with an image in the image-receiving layer is generated tightly. The uncured silver halide emulsion layer is then removed by washing with warm water.

The binder for the silver precipitant can be completely or partially, preferably at least 50% by weight, consist of a protein. Gelatin has proven to be a particularly advantageous protein. However, to produce the The image receiving layer also advantageously uses other commonly known proteins such as casein, zein, albumin and the like will.

109831 / U32

210-08

Gelatine can also be used to produce the image-receiving layers and other proteins can be used in admixture with other polymers compatible with these proteins. Particularly suitable Polymers that can be used in a mixture with gelatin and other proteins are, in particular, so-called terpolymers Ethyl acrylate, acrylic acid and 2-acetoxyoxyethyl methacrylate.

Polymers particularly suitable for producing the image-receiving layers are also the water-soluble quaternary salts of Polyvinyl vinyl compounds, for example from the USA patent 3,174,858 are known. These water-soluble, basic polymeric quaternary salts have a Polyvinyl chain with 2 to about 10,000 monomeric units, with at least one monomeric unit having a 5- or 6-membered heterocyclic nucleus with a quaternary nitrogen atom is bound.

Such a polymer can have, for example, the following structure to be marked:

109831 / U32

where mean:

η is a number from 2 to 10,000;

X is an anion, for example of the formula

CH ₃ SO ₄ or a p-toluenesulfonate anion or an iodide anion;

R is a hydrogen atom or an alkyl radical

1 to 10 carbon atoms, for example a methyl, ethyl, propyl or butyl radical or a halogen atom or a nitro, amino, aralkyl or aryl radical and

R _{1 is} a radical of the meaning given for R,

with the proviso that R * and R are one of each other have different meanings "

The heterocyclic nucleus can optionally also have further heteroatoms. Finally, they can be attached to the polyvinyl chain bonded heterocyclic nuclei may be substituted in other ways than indicated.

Typical polymers used to make the image receiving layer can be used, for example:

Poly (1,2-dimethyl-5-vinylpyridinium methyl sulfate); Poly (I-me thy l-2-vinylpyridinium iodide] J. Poly (1-methyl-2-vinylpyridinium methyl sulfate); Poly (1-methyl-4-vinylpyridinium iodide); Poly (1-methyl-4-vinylpyridinium methyl sulfate); Poly (I-vinyl-3-methyliinidazolium iodide) and Poly (I-vinyl-3-methylimidazolium methyl sulfate).

109831 / U32

210U08 - ίο -

In addition, such polymers can advantageously be used for the production of the image-receiving layer which consist of a polyvinyl chain, at least one Monomer unit of this chain is substituted by a heterocyclic nucleus with a quaternary nitrogen atom and the chain also has at least one linear remainder *

Such polymers can be, for example, starting from a polymerization mixture, the linear compound N-cyanoacetyl-N'-methacrylylhydrazine (according to USA patent 2 940 9S6) of the following formula:

NsC-CH ₉ -C -NH-NH-CC = CH ₀

Il Il I ²

0 0 CH- or

2-Acetoacetoxyäthylmethaerylat, according to Belgian patent 691 446 of the following formula:

CH, = C-CO-CH ₉ -CH ₇ -OC-CH ₀ -C-CH _x

I Il ^{2 2} If Il CH ₃ ο oo

contains.

It has proven to be particularly advantageous to use image receiving layers which contain on a layer area of 0.0929 m O _{1 1} to 80 mg, in particular 0.2 to 5 mg, of a polyvinyl polymer of the types described. For example, 1 g of gelatin can advantageously be used of the image-receiving layer can be replaced by about 30 mg of one of the specified polyvinyl polymers.

109831/1432

210U08 - 11 -

However, image-receiving layers which consist of a protein-free or practically protein-free image-receiving layer are also suitable for carrying out the method of the invention. For example, for setting up a protein-free or substantially protein-free or only x ^ enig protein (for example, only up to 10 ^wt? O) containing image-receiving layer contains a colloidal binder is used which consists of a copolymer which is built up to about 90 to 98 weight .-I from residues of at least one haloalkyl methacrylate in which the haloalkyl residue has 1 to 10 carbon atoms and about 2 to about 10% by weight of residues of an unsaturated polymerizable organic acid having 3 to 6 carbon atoms.

In the case where a so-called integral recording material is used to carry out the method of the invention is, which is applied to a support an image-receiving layer and over it a silver halide emulsion layer contains, it has proven to be particularly advantageous to use what is known as a binder for the silver precipitation nuclei Use latex binders. Styrene-butadiene latices are particularly suitable for producing the image-receiving layers with a ratio of styrene to butadiene units of 65:35 on a molar basis and a solids concentration of about 50 wt. For the production of the image receiving layers, however, it is also possible to use other customary known latices of vinyl or acrylic homopolymers or mixed polymers are used. After this the latex with the silver precipitating agent has been applied to the support, the image-receiving layer produced can with an uncured gelatin-silver halide emulsion layer coated xvorden, whereupon the material obtained in the usual Manner exposed and forming an image in the image receiving layer can be developed. The gelatin-silver halide emulsion layer can then be washed off with, for example

109831 / U32

2Ί0Η08

warm water or the like.

In addition, alkyl acrylates and sulfoalkyl acrylates are advantageously suitable for producing the image-receiving layers built-up polymers of the type known, for example, from Belgian patent specification 691,446. Typical Such polymers consist, for example, of butyl acrylate, sulfopropyl acrylate and 2-acetoxyethyl methacrylate units or butyl acrylate and sulfopropyl acrylate units.

If the image receiving layer advantageously contains an alkaline iodide, for example ammonium, guanidine, sodium, Potassium or lithium iodide can be used in the image receiving layer advantageously in concentrations of about 0.1

up to 20 mg, in particular 0.5 to 10 mg, per 0.0929 m layer area be included. By incorporating an iodide into the image-receiving layer, the tone or the tint of the generated image is further improved.

By adding a silver salt or complex, e.g. B. silver nitrate, for the image receiving layer, the quality of the image generated by the diffusion transfer, for example the image density, can be further improved. The silver salts and complexes suitable for this purpose can be organic and inorganic in nature. A typical organic silver complex is, for example, silver dipyridyl nitrate. Suitable silver salts and complexes are described in detail, for example, in U.S. Patent 3,446,619. Particularly advantageous silver salts are also the silver salts of mercaptotetrazole and mercaptotriazoles and corresponding heterocyclic mercapto compounds, which are known, for example, from US Pat. No. 2,432,864. However, silver nitrate is preferably used. The silver compound can advantageously be used in a concentration of about 0.01 to about 10 mg, preferably about 0.05 to about 5 mg per 0.0929 m ^{2 of} layer area

109831 / U32

210U08

be used.

The coating compositions used to produce the image-receiving layers In addition, all the additives can be incorporated, corresponding to the coating compounds in the usual known manner are added for the production of image receiving layers, for example surface-active compounds, Coating aids, developing agents, release agents, silver halide solvents and the like. This means j that the coating compositions a wide variety of additives can be incorporated with which the image quality in the image receiving layer can be improved. It is also possible to arrange a release agent in a coating layer.

Particularly suitable surface-active compounds and spreading agents to produce the image-receiving layers, for example, saponin, lauryl alcohol sulfate, p-tert-octylphenoxyethoxyethyl sodium sulfonate and the same.

As the silver precipitating agent in the image receiving layer, conventionally known silver precipitating agents can be used. Such precipitants are, for example, from US Patents A

2,698,237, 2,698,238, 2,698,245, 2,774,667, 2,823,122,

3,396,018 and 3,369,901 are known. Silver and precious metals, e.g. B * gold, Platinum and palladium, proven in colloidal form.

Preference is given to using precious metal nuclei as silver precipitants, by reducing a noble metal salt using borohydride or a hypophosphite in the presence of a colloid can be obtained.

The metal nuclei can advantageously be present in the presence a proteinaceous colloid, e.g. B. gelatin

109831/1432

210H08

will. If necessary, another colloid can be added later, namely the same colloid or a colloid different from the colloid used initially can be added. From the manufacturing method the germs results in the coating mass not only the germs themselves but also reaction products which result from the reduction of the metal salt used to produce the germs.

The concentration of the colloid used in the production of the active noble metal nuclei can be very different, depending on the the particular colloid used, e.g. Gelatin, the reducing agent used, e.g. borohydride, and the applied Ratios of the reaction components. They are useful for producing the coating compositions for the image-receiving layer Colloid concentrations of 0.5 to about 20% by weight, in particular 1 to about 10% by weight, based on the weight of the total Reaction mixture, used.

The image-receiving layer expediently contains about 5 to about 500 mg of colloidal binder per 0.0929 m ^{2 of} carrier area · The concentrations of active noble metal nuclei in the image-receiving layer are about 1 to 500 μg per 0.0929 m ^{2 of} carrier area ^{up to about 5 mg per 0.0929 m 2 of} carrier surface can be used · According to a particularly advantageous embodiment, the image-receiving layer has about 30 to 80 wg of active palladium nuclei and 80 mg of colloidal binder (on a solid basis) per 0.0929 m 2 of carrier surface.

The image-receiving layers can be applied in the usual way to conventional, known layer supports, ζ. Β. made of paper, glass, plastic, wood and the like. Those made of paper, in particular made of baryta-coated paper, have proven to be particularly advantageous layer carriers *. Particularly advantageous

109831 / U32

210H08

- 15 -

have also proven to be made of paper, coated with a polymeric substance, e.g. B. polyethylene coated that serves as a moisture barrier. The polymeric substance, e.g. B. polyethylene or another polyolefin, can be pigmented to produce a white surface.

In the usual way, so-called anti-discoloration agents can be added to the supports (Antistain agents), ζ. B. Acid, like her for example known from U.S. Patents 3,250,619 and 3,326,744. Possibly however, the paper backings can also have been coated with polymers other than polyolefins, for example with polyesters, polyamides, polycarbonates, cellulose esters, polyacetals and the like. Finally, the specified Polymers can also be used as layer supports themselves in the form of self-supporting layers.

To improve the adhesion of the image receiving densities the substrate, these can be pretreated in the customary known manner, for example by applying adhesive layers, by electron irradiation, by treatment with a peroxide, and the like. This is especially true for the Case that a photographic film base is used as the support is used.

The image receiving layers can optionally be used in the process The material used in the invention also includes solid particles, for example made of silica, bentonite, diatomaceous earth, z. B. Kieseiguhr, glass in powder form and calcium montmorillonite and aluminum oxide. In the end the layers can also contain colloidal particles of metal oxides, e.g. B. from titanium dioxide, aluminum oxide, zirconium oxide and the like.

109831/1432

210H08

In carrying out the process of the invention, a silver halide emulsion layer is first image-corrected in a conventional manner exposed, whereupon the silver halide emulsion layer is treated with a silver halide resist, e.g., a silver halide developer solution is brought into contact, which contains a compound binding the silver halide complex. the exposed emulsion layer is in the exposed areas developed while the silver halide of the unexposed areas is complexed. When the SiI overhalide emulsion layer is brought into contact with the image-receiving layer, the complex-bound silver halide then diffuses imagewise into the Image receiving layer and creates an image here with the aid of the silver precipitating agent contained in the image receiving layer.

It can optionally be advantageous to use the image-receiving layer in order to improve the stability of the layer, in particular in the With regard to the silver image it contains. A simple method of stabilization is to use the Wash the image to remove chemicals from the development process. However, such washing protects that Do not picture before later chemical reactions with constituents of the atmosphere, e.g. oxygen or hydrogen sulfide, which have an adverse effect on the stability of the silver image. For this reason, the image produced can later be coated are, for example with coating compositions of the type known from US Pat. No. 2,979,477, which form a mixture from a vinyl pyridine polymer and a hydantoin-formaldehyde condensation polymer contain.

To protect the images generated in the image receiving layer, you can the images also optionally with methylraethacrylate-methacrylic acid copolymers or with the combination of a polymer containing acidic radicals or sulfate radicals,

108831 / U32

such as a copolymer of methyl methacrylate and methacrylic acid and a hydantoin-formaldehyde condensation polymer of the French patent 1,493,188 known type are coated. If appropriate, the coating compound used for coating can also a heavy metal salt such as zinc acetate may be incorporated. Further improvements in the durability of the images produced can optionally be achieved by adding an acid, e.g. B. acetic acid or propionic acid, is incorporated.

The conventionally known silver halide developing agents can be used to develop the exposed silver salt layers of the material used in carrying out the process of the invention. As complexing agents for the silver salt, the conventionally known silver halide solvents or "silver salt complexing agents", e.g. The concentration of developer compound and / or developer precursor compound which can optionally be used instead of the developer compound is preferably from about 3 to about 320 mg per 0.0929 m ^{2 of support area} .

The developer compounds and / or the corresponding so-called developer precursor compounds can optionally be used in Form of a viscous, thickening agent, e.g. B. carboxymethyl cellulose or hydroxyethyl cellulose containing developing solution can be used. Typical developer solutions for carrying out the method of the invention are known, for example, from US Pat. No. 3,120,795.

109831/1432

The developer compounds and / or developer precursor compounds can be used alone or in combination with one another or together with so-called auxiliary developer connections will. Typical suitable silver halide developer compounds and developer precursor compounds used to carry out the Processes of the invention which can be used are, for example, polyhydroxybenzenes, substituted by alkyl radicals Hydroquinones, e.g. B. t-butyl hydroquinone, methyl hydroquinone, 2,5-dimethylhydroquinone, catechol and pyrogallol Chlorine atoms substituted hydroquinones, e.g. B. chlorohydroquinone and dichlorohydroquinone, hydroquinones substituted by alkoxy radicals, e.g. methoxyhydroquinone or xthoxyhydroquinone, aminophenol developer compounds, e.g. 2,4-diaminophenols and methyl aminophenols. To the particularly suitable developer compounds also include 2,4-diaminophenols, which are substituted in the 6-position, and related amino developer compounds, for example:

6-methyl-2,4-diaminophenol, 6-methoxy-2,4-diaminophenol, 6-ethyl-2,4-diaminophenol, 6-pheny1-2,4-diaminophenol, 6-p-tolyl-2,4-diaminophenol, 6-chloro-2,4-diaminophenol, 6-morpholinomethyl-2,4-diaminophenol, 6-piperidino-2,4-diaminophenol, 3,6-dimethy1-2,4-diaminophenol, 6-phenoxy-2,4-diaminophenol, 2-methoxy-4-amino-5-methylphenol, 4-aminocatechol, 4-axonoresorcinol, 2,4-diaminoresorcinol, Methyl-3,4-diaminophenol, Methoxy-3,4-diaminophenol,

108831 / U32

210U08

Methyl-2,5-diaminophenol,
Methoxy-2,5-diaminophenol,
Methyl-1,2,4-triaminobenzene, p-hydroxyphenylhydrazine and
p-Hydroxypheny / hydroxylamine.

The aminophenol developer compounds can optionally be used in Form of an acid salt, ζ. B. as a hydrochloride or sulfate salt, be used.

Other suitable silver halide developing agent compounds which can be used to carry out the process of the invention are, for example, ascorbic acid, ascorbic acid derivatives, ascorbic acid ketals, for example of the type known from US Pat. No. 3,337,342, hydroxylamines, e.g. B. N, N-di (2-ethoxyethyl) hydroxylamine, 3-pyrazolidone developer compounds, e.g. B. 1-phenyl-3-pyrazolidone, including the compounds and acyl derivatives of p-aminophenol known from British patent specification 930 572, as are known, for example, from British patent specification 1,045,303. Also suitable are pyrimidine developer compounds, e.g. 4-amino-5,6-dihydroxy-2-methylpyrimidine, and aminomethylhydroquinone- A silver halide developing compounds, e.g. B. 2-methyl-5-pyrrolidinomethylhydroquinone, 2-methyl-S-morpholinomethylhydroquinone and 2-methyl-5-piperidinomethylhydroquinone. The aminomethylhydroquinone silver halide developer compounds are particularly suitable for incorporation into the negative material used to practice the method of the invention.

As suitable silver halide developer compounds for implementation of the process of the invention are also to be mentioned the silver halide developer compounds consisting of reductones, in particular the well-known anhydrodihydroaminohexosereductone-silver halide developer compounds, z. B. anhydrodihydropiperidinohexose reductone, anhydrodihydropyrrolidinehexose reductone and / or anhydrodihydromorpholinohexose reductone.

109831 / H32

210U08

The silver halide developer compounds consisting of reductones can be different in the context of the diffusion transfer process, i. H. in different places to use to be brought. It has proven to be particularly advantageous to use them in the solution used for development. The silver halide developer compounds consisting of reductones can be used alone or in combination with used by other developer associations for development. A particular advantage of using these developer compounds is based on the fact that when they are used, only very little or no color haze or discoloration are produced and that furthermore an improved image stability is achieved.

Particularly suitable developer compounds for carrying out the process of the invention are furthermore made from lactone derivatives existing silver halide developer compounds, which have the property of being so-called T under neutral and acidic conditions To form developer precursor compounds. Such silver halide developer compounds consisting of lactone derivatives are particularly advantageous because they not only develop the desired development activity, but also lead to a strong reduction or elimination of color haze and discoloration without D and D. who have favourited photographic To adversely affect the sensitivity and other desirable properties of the photographic material. Particularly suitable developer compounds of this type are those which are below neutral, weakly alkaline or acidic conditions, d. H. when the pH is reduced to about 9 or below; d. H. about 2 to about 9, no ins Exercise weight-decreasing developmental activity due to the formation of a so-called precursor compound.

109831 / U32

210H08

The photosensitive materials used in carrying out the method of the invention can be incorporated in their photosensitive layers, e.g. B. silver halide emulsion layers contain conventional additives, e.g. Chemical sensitizers and spectral sensitizers, coating aids, antifoggants, and the like. Furthermore, they can optionally also contain silver halide developer compounds or precursor compounds which produce silver halide developer compounds. If necessary, the compounds required for developing the material can also be contained in a layer arranged adjacent to the silver% halide emulsion layer.

In the case of the light-sensitive emulsion layers of the implementation The material used in the method of the invention can also be X-ray layers or other non-spec. act trally sensitized emulsion layers.

Typical suitable spectral sensitizing dyes for sensitizing the layers are cyanine, merocyanine, Styryl and hemicyanine dyes. Reference is made, for example

to U.S. Patents 2,526,632 and 2,503,776. g

The emulsion layers of the photographic material used in practicing the process of the invention can be des further hardened in the usual way by hardening agents, for example hardening agents from the British 974,317 known type. Finally, they can contain buffer substances which have the desired development activity maintain the developer compounds and / or maintain the desired pH range. Furthermore, the Emulsion layers contain, for example, plasticizers, additives which increase sensitivity, e.g. B «amines, quaternary ammonium salts, sulfonium salts and alkylene oxide polymers

109831 / U32

210H08

and a wide variety of stabilizing agents such as sodium sulfite. The silver salts of the photographic layers, particularly photographic emulsion layers, can be of the broader type chemically with various sulfur, selenium and tellurium compounds, precious metal salts, e.g. gold, or reducing agents or combinations thereof. For the production of the photosensitive silver salt layers the most varied of customary photographic silver salts, in particular silver halides, e.g. silver iodide, Silver bromide, silver chloride, as well as mixed halides, e.g. silver bromoiodide, silver chloroiodide, silver chlorobromide and Silver bromochlone iodide, used in animals. Not from silver halides existing photographically active silver salts which are suitable for the preparation of the light-sensitive layers the silver salts of organic acids, silver dye salts or complexes.

The silver salts are preferably in a conventional one Binders of the type used for the production of photographic emulsion layers are pre-dispersed. Typical suitable Binding agents for the production of the emulsion layers are gelatine, colloidal albumin, water-soluble vinyl polymers, mono- and polysaccharides, cellulose derivatives, proteins, water-soluble polyacrylamides, polyvinylpyrrolidone and the like, v / ie also Mixtures of these binders.

The photographic materials used to carry out the method of the invention can furthermore have so-called separating layers and / or antistatic layers, ie conductive layers.

109831 / U32

210U08

Resin-like or polymeric substances are particularly suitable release agents for facilitating the separation of the image-receiving layer having a molecular weight of about 10,000 to about 500,000, e.g. that of U.S. Patents 3,169,946, 3,007,901, 3,206,312, 3,260,706, 2,306,071 and 3,102,028 of known type. These substances are lactones from resinous heteropolymers of vinyl or isopropenyl acid esters of an unsaturated α, β-dicarboxylic acid, those with a monobasic alcohol or a mixture of a monobasic hydroxy acid and a monobasic Alkanol have been implemented. '

Relatively thin layers can be produced from these polymers, e.g. layers with a layer thickness of preferably

2
about 6.0 mg per 0.0929 m support area. In general, however layers using a \ ^r on such polymers

Thickness of about 1.0 mg to 1.0 g per 0.0929 m of support area produced will. ; \ "As already explained, the release agents can, however, also be used in the image receiving layer itself together with the Silver precipitants can be used.

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

109831 / U32

210U08

example 1

First, a Kdmschmelze was produced as follows:

1.) 138 g of an oily bone gelatin were in 862 ml entered distilled water.

2.) The mixture was heated to 50 ⁰ C, followed by 7 ml of a 1,24ligen PdCl - solution (1% HCl) was added.

3.) The pH value was increased to 6.0 by adding sodium hydroxide set.

4.) Now 30 ml of an O, 2ligen NaBII solution (60 mg) added, whereby the PdCl- was reduced to colloidal palladium. The pH rose to 8.3 to 8.5 at.

5.) The melt was then stirred at 50 ° C. for 10 minutes. The pH was increased by adding 0.1 η hydrochloric acid 5.5 set.

6.) There were 562 g of 10 oily bone gelatin and 438 ml added distilled water.

7.) It was stirred further and allowed to cool. Aufxaticse

Using the seed melt produced, a total of 5 coating compositions were produced, the composition of which is shown in the table below. These coating compositions were then applied to polyethylene-coated paper backings in such a way that 2.5 nil of the melt were accounted for ^{on a carrier area of 0.0929 m 2, corresponding to a gelatin coating of 13.25 mg and one}

109831 / H32

2Ί0Η08

1 mg potassium iodide coating as well as a silver nitrate coating of 0.08 mg and a phenylselenotetrazole coating of 0.08 mg, each per 0.0929 m of support area.

ml 2 Test item 3 No. 4th ml 5 ml 1 • 1 48 48 48 dd 48 Il 48 It 252 ml 252 ml 250 ti 252 Il 250 Il 5 ti 5 It 5 Il 5 It 5 • 1 2.5 ti 2.5 Il 2.5 It 2.5 ti 2.5 • 1 3 Il 3 It 3 3 3 Il 1.3 Il 1.3 M. M Ml It - 1.3 ti - ti - dd S. Il - ti 5 1 mm wm 1 1 1 It

^^ w JbIIIw ^ llJliC J · £ t wr% * «ltd · T ^ * ·» «it ^ ~ * w aia ^» τ w nt «· w **, ** ^ *

distilled water ^ηρΛ " ^or " ^fI " ^{r #} » " * ^rn "" ^Γη "'

1% poly (1,2-dimethyl-5-vinylpyridinium methyl sulfate

10% formaldehyde
15% saponin
10% potassium iodide
0.2% silver nitrate

1% i-phenyl-5-seleno-1,2,3,4-tetrazole

On the image receiving layers produced in the manner described separating layers were then applied, namely in a coating thickness of 3 mg per 0.0929 nr carrier surface from coating compounds of the following composition:

Sodium salt of carboxybutyl ester lactone

a polymer of maleic anhydride

and vinyl acetate (11.27 wt%) 29 ml

distilled water 500 ml

Methanol 2250 ml.

10 9831 / U32 _OBISlf4AL , _NSPECTE0

210H08

The obtained image receiving materials were then thereby
tested that they were brought into contact with a silver bromoiodide emulsion layer previously applied to an opaque
Support had been applied. The emulsion layers were then exposed in the usual manner and with a viscous developing solution of the following composition:

g / l

6-methyl-2,4-diaminophenol sulfate Max ter-butylhydroquinone 1.60 Na ₂ S ₂ O ₃ . 5H ₂ O 1.36 NaOH 1.48 KOH 1.12 AI 1.10 Hydroxyethyl cellulose K ₂ Sun ₃ developed. Results: Test item 1 2 3 4th 5

5-10 25th 60 20th 20th 0 , 6-1.6 3 -4.51 25th -50

tint

cold

cold

warm

neutral

neutral

109831 / U32

2T0U08

Example 2

Other image receiving materials were prepared as indicated in Example 1 under Sample No. 1, with the exception however, that instead of 1-phenyl-5-seleno-1,2,3,4-tetrazole other tetrazoles were used.

After using the image receiving materials produced according to the method described in Example 1, the washed images were placed in a lockable chamber at a temperature of 43 ^° C. and a relative humidity of 851 for 6 days and irradiated with 19,370 lux of white light using a fluorescent lamp. The following results were obtained:

Tetrazole

1-phenyl-5-seleno-1,2,3,4-tetrazole

tint Max stability black 1.56 barely noticeable Change of cold image tone, Loss 1 level des Step wedge in the through slope area of the H- and D curve

1-phenyl-5-mercapto 1,2,3,4-tetrazole

5,5 »-dithiobis (1-phenyltetrazole)

black 1.56 significant warming of the tone, loss of 3 levels in the sagging area

black 1.58 significant warming of the tone, loss of 3 levels in the sagging area

109831/1432

210H08

black 1.50 essential erthio) -1-phenyltetrazole warming of the clay,

Loss 1 level in the slack area

The reference to the steps in the slack area relates to the usual well-known H and D curves used for silver halide emulsions is characteristic and increments of 0.15 log Ε units or an increment of 0.15 log Ε units for 1 stage.

Example 3

The procedure described in Example 1 was repeated, but this time instead of 1-phenyl-5-seleno-1,2,3,4-tetrazole the compound 1-allyl-S-seleno-i, 2,3,4-tetrazole is used became. Again, neutrally tinted images were obtained.

Example 4

Further image-receiving layers were produced as described in Example 1 under test specimen No. 5, but this time other 5-seleno-1,2,3,4-tetrazoles of the following formula are used became:

See

R N

N - = r N

where R is a methyl, ethyl, butyl, decyl, Phenyl or tolyl radical possessed. The image-receiving layers formed were then prepared in the manner described in Example 1

109831 / U32

210U08

tested. Neutral tinted images were obtained in all cases.

Example 5

Using the seed melt described in Example 1, further image receiving materials were prepared, "with the The exception, however, was that no 1-phenyl-5-seleno-1,2,3,4-tetrazole was used for the production of the image-receiving layers.

The image-receiving layers were prepared by applying the coating compositions to a polyethylene-coated one

Paper carrier with a thickness of 2.5 ml per 0.0929 m carrier surface, which is a coating of 13.25 mg gelatin, 1 mg

2 potassium iodide and 0.08 mg silver nitrate per 0.0929 m support area corresponded. As described in Example 1, a release layer was then applied to the image-receiving layer.

The image receiving material obtained was then tested by that it was brought into contact with a silver bromoiodide emulsion layer which had previously been applied to an opaque support was and had been exposed. After the imagewise exposure, the emulsion layer was torn open Tear-open container with the developer solution specified in Example 1 developed. In contrast to the one in example 1 However, the developer solution described here contained 0.1 ml of a Uigen 1-phenyl-S-seleno-1,2,3,4-tetrazole solution per liter of developer solution.

The diffusion transfer image had a D _max of 1.60 and a cold tone similar to the images obtained in Example 1.

109831/1432

This example shows that the selenotetrazole can also be used in an advantageous manner in the developer solution.

109831 / M32

Claims (9)

210U08 - 31 - Patent claims 1. Photograpliiscb.es diffusion transfer process in which that in the development of an exposed silver salt-containing photosensitive layer of a photographic Recording material undeveloped silver salt on a an image-receiving layer containing silver precipitating agent is transferred, characterized in that the (| drive in the presence of a 5-seleno-1,2,3,4-tetrazoles. 2. The method according to claim 1, characterized in that the 5-seleno-1,2,3,4-tetrazole in the image receiving layer used. 3. The method according to claim 2, characterized in that one in the image receiving layer based on a layer area of 0.0929 m ² (
tetrazole used '. 0.0929 m ² based on 0.01 mg to 0.5 g 5-seleno-1,2,3,4- 4. Process according to Claims 1 to 3, characterized in that an image-receiving layer is used which contains a silver halide solvent and contains a silver halide developing agent. 5. Process according to Claims 1 to 4, characterized in that that one to carry out the process a photographic Material used in which the image-receiving layer is on a support under a photosensitive silver halide emulsion layer is arranged. 109831/1432 6. Process according to Claims 1 to 5, characterized in that an image-receiving layer is used, the silver precipitating agent thereof consists of a noble metal present in colloidal form. 7. The method according to claim 1, characterized in that the 5-seleno-1,2,3,4-tetrazole in the development of the Recording material used developer solution used in concentrations of 0.01 to 1.0 g per liter of solution. 8. Process according to Claims 1 to 7, characterized in that a 5-seleno-1,2,3,4-tetrazole of the following structural formula is used used: See = N R - N N = N wherein R is an alkyl radical with 1 to 10 carbon atoms, an aralkyl radical with up to 10 carbon atoms, an alkenyl radical with up to 10 carbon atoms or an aryl radical of the phenyl or naphthyl series. 9. Process according to Claims 1 to 7, characterized in that the 5-seleno-1,2,3,4-tetrazole used is: 1-phenyl-5-seleno-1,2,3,4-tetrazole or 1-allyl-5-seleno-1,2,3,4-tetrazole. 109831/1432