DE1547986A1 - Photographic recording material - Google Patents

Description

"Photographic recording material"

The invention relates to a photographic material with which the Production of visible images, in particular silver images, optionally after transferring them to an image according to the image Image-receiving element based on a silver halide. emulsion is possible. - '.

Most of all silver halide photographic processes use the unexposed silver halide dissolved and the exposed emulsion layer removed simultaneously with or after development. The preferred one Dissolution of the unexposed silver halide substantially simultaneously with development of the latent image is the basis of a number of photo processes, in particular

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other the silver salt diffusion transfer method (USA patent 2 ί? 43 181; "A New One-Step Photographic Process" by Edwin H. Land, Journal of the Optical Society of America, Vol. 37, pp. 61-77, February 1947; "One-Step Photographic" by Edwin H. Land, The Photographic Journal, January 1950, Ne7-15). The dissolved silver complex is transferred to another solute and precipitated there and thus becomes a positive one Silver transfer image built up *

It has now been found that if a silver halide grain is exposed sufficiently to render it developable, and Developing with a composition containing a silver halide solvent and a Silberhaj-Ogenid developing agent besides usual components in which grain the speed the development and the speed of dissolution in compete for the grain. Is now the speed of development and the dissolution of the developing silver halide adjusted in the grain so that at the place of the inner development the dissolution of silver halide takes place preferentially, ao one has a completely new basic principle of a photographic one Procedure. This is because unexposed and undeveloping silver halide remains undissolved, so you could refer to this new process as "resolution development". The developer intervenes for a given exposure time only the silver halide grains which have started to develop.

As mentioned, it was found that the speed the development and resolution is adjustable so that developable silver halide in an exposed grain in the

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Developer composition is preferably dissolved. This setting can be activated, for example, by a corresponding concentration Silver halide solvents. The difference between development and dissolution speeds may optionally be relatively kledji, e.g. if only they rely on the concentration of the silver halide solvent is based to obtain development by dissolving. However, this difference can be modified by applying a promoter or accelerator for dissolving development. ' *

The photographic material according to the invention is about conventional silver halide emulsions, which can be used for conventional, but often also significantly lower, exposure. That The basic principle of the invention is that a developing syllable rhal ο genidkorn dissolves much faster than Grain that has not yet developed, one to develop preferentially can dissolve and become usual in this way Silver halide emulsions can be used in diverse, new and extremely useful ways and depending on the exposure either negative or positive or even partially negative and partially positive image With regard to the latent image obtained can. This also applies in particular to silver salt diffusion transfer processes.

In the case of the photographic material according to the invention, the preferred one takes place Dissolution of silver halide in or from the exposed grain of the silver halide emulsion layer in the sense of an imagewise Development of the exposed grain; the extent * of the dissolution of a developable grain depends on the exposure. -

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In. in phototechnology it is generally customary that the exposed silver halide is made insoluble, e.g. by preferential and selective reduction of the exposed Silver halide in the latent image to silver. Both known special silver halide emulsions, e.g. so-called emulsions with an internal latent image unexposed silver halide developed faster than exposed; require such silver halide emulsions special conditions for development, they have a relatively low photosensitivity and are therefore referred to only as slow working materials.

In the inventive photographic material usual silver halide emulsions are used, and these in the usual manner a latent image by exposure -on overall <■ £ -_ bautj used for processing usual J silver halide developer usual. Alkalis, * silver halide complex builders or solvents. According to the invention, however, the developability and dissolvability of a silver halide grain is adjusted so that, for a given exposure, the initial development of exposed silver halide leads to a much faster or more extensive dissolving of exposed silver halide than of unexposed silver halide. If the exposure exceeds the value which is necessary for the developability of the grain and for this initial development, the grain will develop further into silver, making it insoluble. At a given exposure, an unexposed and therefore undeveloped grain is insoluble in the developer within the development time; , a ^J fully developed grain. is insoluble because it - only

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Is silver, and a partially developed grain is partially. wise soluble. In common photographic systems nothing more is achieved if one is responsible for development "Sufficient" exposed grain is exposed beyond the minimum exposure required for this. In contrast in addition, one appears in the photographic material according to the invention Exposure above the minimum eat developability and dissolvability to change, the silver halide exposed in this way can be developed more quickly or has several grains developable districts or domains. One advantage of the photographic material according to the invention, e.g. for the production \ a negative transfer image, lies in the dissolvability of the silver halide grain by combining the minimum exposure necessary for development capability and the first stages of actual development. These Minimum exposure ^ is really very low and is' often smaller than that for a specific negative material is usually specified.

As mentioned above, the / relative developability is and solubility of the silver halide grain, adjusted so that as a result of the initial development the solubility of the Silver halide is catalyzed where the development is takes place so that silver halide preferentially in exposed areas, i.e. at a much faster rate dissolved as silver halide in unexposed areas will. These speeds can be set at different Way of influencing a balanced system, preferred the latent image in. . Presence of a combination a ä); Silver halide solvent and b) promoters or accelerator for solubility to development

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treated. - or called solubilizer for short - ^ \ This combination leads to the dissolution of "of" exposed ones much faster Silver halide on which development has already started than on unexposed one.

The solubilizer in the context of the invention is a substance which, under appropriate conditions, together with a silver halide solvent, brings about the preferred dissolvability of the exposed silver halide, that is, after minimal exposure for the onset of development. The exact mechanism of the reaction is not yet known. There are a large number of substances that are effective as solubilizers. These substances exhibit many common properties when used in conventional wet developing processes. However, none of these properties are essential for the solubilizer, so it may not be necessary to have them * Nonetheless, the presence of one or more of these properties can be used to select further solubilizers. One of these properties is the ability to form a salt or complex with the silver ion or silver halide; it is known that many substances form largely water-insoluble silver salts. Many solubilizers contain the

Grouping:.

SH SH SH

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(or their tautomeric forms). Most of these connec- Fertilizers act in the appropriate concentration as a development inhibitor and / or antifoggants, a number of which have been used as toners in positive silver diffusion transfer images been applied. In general they are

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but used as a solubilizer according to the invention in greater concentrations than for antifoggants, toners, etc. To determine whether a substance is suitable as a solubilizer in the context of the invention, it can be given to the developer in a diffusion transfer process. which contains a silver halide solvent, preferably an alkali thiosulfate - with normal exposure-mart-. a positive silver transfer image is obtained. If a solubilizer is present, you can see that if you increase his »-ee & ea? Concentration comes to a value at which the transfer of unexposed silver halide is essentially interrupted, but the. negative development is not prevented. At this value, the concentration, the silver halide solvent and the development time increase until a negative or a negative / positive silver transfer image is obtained. If you get a negative / positive transfer image, lower exposure leads to a negative sirber transfer image *. ■■ '■■'. :

Although compounds can be used as solubilizers which inhibit the development and these are present according to the invention in concentrations which are much greater than. As they are used as development inhibitors in conventional photographic systems, the silver halide remains developable and generally with even higher sensitivity, although the development rate may decrease.

After exposure to a conventional silver halide emulsion, preferably with a higher exposure index than usual developed according to the invention ». The silver halide in the exposed and developable areas very quickly, however

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dissolves very slowly in unexposed areas. Of the ' The soluble complex formed will deposit silver in the presence of a silver precipitating agent, in other words it can in the exposed areas the sirber halide emulsion complex dissolved silver halide elsewhere. be precipitated, especially in one of the original exposed silver halide grain different area.

This type of transfer offers many advantages, one gets e.g. a fixed negative image of high density and high contrast from such a thin silver halide emulsion layer, that with normal development it gives relatively moderate density and contrast. After dissolving the silver halide the unexposed remains in the exposed areas Silver halide probably in complex form, but still light-sensitive, back. When developing ei ^ jer such silver halide emulsion then broken off and put in the darkness is fixed. "is obtained in the silver halide emulsion layer a negative image and also the negative transfer image. One way to make a positive image in the silver halide emulsion layer without special reagents is that that in the emulsion layer remaining unexposed silver halide after removal of exposed silver halide. ^. e.g. an overall exposure or a treatment to make it developable make, is exposed. A usual one can be used to develop the positive image from the non-image areas Use bath. To build up the silver image, only one reducing agent, the lein Silberhalogenidentid-ckler, can be added needs to be use. - · "..".

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Uis iL a "special feature of the photographic material according to the invention that after determining the conditions for the" preferred dissolution of the exposed silver halide from the grain "at a" certain exposure "at higher exposure values, a development of the exposed silver halide and thus the transfer can be achieved in situ Another feature of the photomaferial according to the invention is that at higher exposure values while preventing dissolution, a different developer compound, e.g. lower concentration of silver halide or higher concentration of solubilizer, again achieves preferred resolution and transferability of the exposed silver halide can. This relationship between the various factors such as exposure _r values, development time and processing composition, concentration of Silberhalogehid-Lösungsmitteis or Iiösungsvermittlers like. offers many variations respects borrowed the desired type of image.

The effectiveness of the photographic material according to the invention is likely are based on the following principle: There is unexposed and therefore undevelopable silver halide grain in the developer composition completely absent, on the other hand initially developed Grain easily soluble. This would result in the following: unexposed silver halide grain is not dissolved and is therefore also non-transferrable, excessive exposure leads to complete development and makes JBL possible no transfer. Eventually one would expect through longer exposure to the developer composition the unexposed Silver halide grain will loosen, transfer, and result in dense transfer images; ■ correct exposure would only lead to initial or partial development.

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lead and this properly exposed silver halide would preferentially dissolve. In summary, it follows that that suitable exposure for a conventional image motif for the preferred resolution of exposed silver halide and, in the case of a diffusion transfer process, results in the formation of a negative transfer "false". It can be seen that with the fiction according to the photographic material negative and positive transfer images can be obtained with approximately the same exposure values the positive and negative transfer images reach their highest density. ·

The unexposed grain is not dissolved because of that The rate of dissolution in the developer composition is too slow for a noticeable dissolution within the given time is. Development begins on the exposed silver halide grain. Due to the adjustment made by the The already developing grain is more soluble at the rate of dissolution and development. The proportion of insoluble silver that was formed during development increases with it the amount of light absorbed by the grain. Up to the intersection of the speeds of development and dissolution silver formation does not increase as rapidly as the dissolution and diffusion of the silver halide. Lies however, the exposure value and the developing speed are so high that it is reduced, so becomes essentially the whole Amount of soluble complex of silver halide formed in the strongly exposed grain in the same place as silver reduced and not transferred to another location. It will suspects that these high exposure values lead to nucleation proportional to the exposure and that these nuclei do that

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dissolved silver halide voa dem. Grain "peel off" and become one Direct precipitation on the spot. From this it follows that the can be removed from an exposed grain Amount of silver halide in a diagram 'versus' exposure; value can be plotted and a characteristic curve is obtained for each grain.

For a given exposure value, one or more groups of silver halide grains of similar grain size and / or sensitive wedge are obtained; ₉ which can initially be developed, the type of transmission image shows this mixture. It should be pointed out that the type (of the scale) of the transfer image obtained with the photographic material according to the invention is determined by the amount of light supplied to the grain. In contrast, the conventional photographer! e the type of image from the grain size distribution; A high-contrast image is only obtained if an emulsion has a uniform grain size. With the photographic material according to the invention, these two types can even be superimposed.

The possible types of transfer images from the invention Photographic materials can be created by mixing grain groups certain sensitivity "b. Each grain group lower sensitivity becomes the area for negative transfer image before reversal for positive image .extend. For this, however, the same should be as possible for grain groups of different sizes or sensitivities Solvability and developability exist. Bigger ones Emulsions with grain groups of different sensitivity one gets by mixing "sensitized and unsensitized." Grains of the same size

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The photographic material according to the invention can be negative, positive or negative / positive Receive transmission image. It should be noted that the positive transfer image to completely others Way than in conventional positive silver transfer processes. That is where it becomes positive built up from the unexposed silver halide, whereas according to the invention all of the image silver is available for transmission.

In a silver halide emulsion there are always a number of with additional exposure. Silver halide grains which become developable as a result of their size and / or sensitization. If the number of grains _A which can be developed by increasing exposure is plotted against exposure in a diagram, silver halide emulsions which are suitable for cameras show a generally bell-shaped sensitivity distribution curve. This curve shape results from the fact that with the lowest exposure a small or minimal number of grains, namely the most sensitive, are exposed and developable, with increasing exposure

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evaluate, x-i increases the number of additional developable grains to a maximum, which represents the mean sensitivity, thereafter every further increase in the exposure values will make fewer and fewer grains developed, Ms again ■ a minimum "is reached for the less sensitive grains. ^! - . ■

For a negative transfer image using the Photographic material according to the invention one needs exposure values, the lowest some grains and the maximum Value makes a maximum number of grains initially developable. For me a positive transfer image "you need exposure value e'j whose minimum corresponds to the maximum developable number of grains. The positive transfer image obtained according to the invention does not maintain its maximum density of all grains of the silver halide emulsion (as in conventional silver transfer processes), but of one Grain fraction that is between the high number middle Sensitivity and the lower number lesser · Sensitivity lies. The decrease in image density with increasing exposure is therefore two factors in the positive process attributable to: 1.) development of an increasing grain number to silver in place and 2.) the reduction with initially developable grain number with increasing exposure.

With the same developer composition, according to the invention, either a negative or a positive transfer image can be obtained received, this depends on the distribution of the initial developable grains. For each grain there is a critical exposure, i.e. a usable but reasonable one small exposure value at which part of this

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Korns becomes dissolvable and transferable. Given the exposure lead only the .developable Grains for blackening; therefore, the density of a transfer image results from the distribution curve, i.e. the height the distribution curve mentioned. The image density is therefore a function of the total number of grains for a given exposure of a given size and / or sensitivity. After According to the invention, one can change the shape of the blackening curves of the transfer image by increasing the number of silver halide grains of a given size and sensitivity.

It is of particular importance that the dissolved silver halide in the photographic material according to the invention does not turn into silver must be reduced. These new complexes of exposed silver halide are quite stable to reduction, even with respect to them Silver halide developers, even in the presence of alkalis; However, it can be reduced to silver by he came into contact with a silver precipitating substance, such as it is customary in the transmission process.

The terms "latent image", "negative image" and "positive image" are used here with their usual meanings. If a silver halide emulsion layer is exposed to actinic light through a negative, a positive is produced By precipitation of transferred soluble complexes of the exposed silver halide, a positive silver image is obtained. . /

Any one can be used in the photographic material of the present invention Silver halide developers such as hydroquinone, 4 ~ N-methylamino-phehol (Metol), ascorbic acid, iso-ascorbic acid, ' 2,6-dimethyl-4-aminophenol, iColuhydroquinone, 2,6-dimethyl-

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hydroquinone> 2-methyl ~ 4 ~ amino-6-methoxyphenol, 2,6-dimethoxy-4-aminophenol, 2,5 ~ -dimethyl-hydroquinone, 2,4 ₅ 6-triaminophenol-2,4- Use Diamino-pla © Hol (Amidol), ϊί, Ιί-Diethyl-hydroxylatiiin, ^ -, G-Biamöno-ortho-Eresol.

The developing liquid contains a silver halide complexing agent or a solvent as commonly used in positive silver transfer processes, e.g. sodium thiosulfate, Potassium thio sulfate, barbituric acid, or uracil, the with the unexposed silver halide: a diffusible one Can form complexes or in the usual way alkalis such as sodium hydroxide, potassium hydroxide or methylamine.

According to the preferred embodiment of the piiotomaterial according to the invention, the developer composition also contains the solubilizer. As already mentioned, substances which can be used as solubilizers are also antifoggants as development inhibitors or toner has been effective and applied in small amounts in known processes such as 1-ehenyl-5-mercaptotetrasol in very small amounts for positive ■ Silver transfer process.

As examples of the solubilizers according to the invention are mentioned:

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■ Ή Ό — ß " Well

IT

1-phenyl - ^ - niercaptotetrazole Nat riiim-1-phenyl IH-tetrazole-5-inercaptan

H ι

C Ν

G

O-SH

4-eth; y-l-2-mercaptO-

1-naphthyl-5-mercaptotetrazole oxazoline

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HOl H-C C-SH H-C H

CH ^

6-1x ^ x0-2- (2'-oxacyclohexarLO.) - benzimidazole hydrochloride 2-mercapto-4-methylpyrimidiii-hydro chloride

H-C

/ Λ.

CH-,

HO — C

0-SH

2-mercapto-6-azatiracil

OH
^: C-

'■■>' / Λ

1 L

H, 0-0 G-SH

³ -ν. ;:

H ₃ C-C

G-SH

4,4-dimethyl-2-mercaptothiazoline

OH I
C.

0-rSH

methyl-pyrimidine.

5,6-dimethyl-4-hydroxy-2-beer captopyrimidine

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OH

GH,

C. G N G / Ii I. / ν G G-SH Η — Ο Η \ / I ι HC-O. 0-SH \ / ^ ff

HGl

4-hydroxyl-2-mercapto-6-phenyl-pyrimidine 4,6-dimethyl-2-mercaptopyriiaidin hydro chi or i d

OH

G-SH

3-Mercapt o-8-tMa ~ 1,2,4-a triazacyclopent (a) indene 8-azaxanthin

5-nitroindazole

N.

6-Benzylaminopurine 909851/0987

-

H-— -G

.H

__; N — Ο — SH

N I

2 ~ mercapto-4mettiyl-imidazole 3-mercapto-4-pkenyl-5-methyl-1,2,4-triazole

J!

; ν

N 0-SH

■ - «0-

2 ', 5-Dimexcapto-i, 3,4-thiadiazole

2-mercaptoethyl sulfide

Tlii oliariis t of f

SH

It

HI

1 -.P3ienyl-5- "benzoylmercapt ot'etrazole ■ '■.

HS

2,6-Dimercapt opuriii 20 -

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HjC -

I I

α c-SH

4-methyl-2-mer c ap t othiazoline

CO-SH

2-mercapto-5-furyl-1,3,4-oxadiazole

II

Benzotriazole 6-nitroindazole

Ο — SH

2-benzoxazole thiol

C-SII

^ -MerCaptobenzotliiazole

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It is true that the exposed silver halide can be treated with a corresponding Amount of a silver halide solvent such as Sodium thiosulfate, preferentially dissolve, but this is not as effective as a combination of a silver halide solvent and a solubilizer, this combination is particularly useful for negatives and the use of silver precipitating agents Means applicable and results in greater image densities and faster developing products. ■

The terms "sensitivity" or "development speed of a photosensitive material" and "exposure index" are often used here. Under the "sensitivity" or "speed ¹¹ of a photosensitive material is generally understood an empirically group derived relative value that is the inverse of that required to achieve the desired result exposure. From" American Standards Association "were recently guidelines photosensitive for evaluating materials published According to this, "Emulsion Sensitivity" or "Emulsion Speed" is inversely proportional to the minimum exposure value for negative material from an object or subject of minimal lightness to see details to produce excellent images. These guidelines also cover the creation of density or gradation curves (H&D curves) of a negative material in which the logarithm of the exposure of the negative is plotted against the blackness or density (density) The numerical value of the sensitivity or speed from this curve is equal to the reciprocal value of the Be exposure value E, at which the increase is 0.3 times as large as the increase in the range log E = 1.5 »if E is the minimum exposure (ASA Publication PH 2.5 .-. 1954, American Standard Method for Determining Photographic Speed and Expo "sure Index").

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The A.S.A. sensitivity or speed value must be distinguished from the A.S.A. exposure index for light meters and exposure indexes. The A.S.A. exposure index is 1/4 of the A.S.A. speed. This exposure index generally gives the correct exposure with an A.S.A. exposure .knife for high quality images. . '

The A.S.A. Sensitivity or Rate Value is further from the "Diffusion Transfer Exposure Index." process ". In the case of diffusion transfer processes, the exposure index can be derived from the curve of the exposure of the negative can be used against the density of the transfer positive. The exposure index at Diffusion transfer method can be determined from the blackening curve (blackening with reflection or transmission against log E of the negative emulsion 0.50 above fog or above

A photomaterial according to the invention is preferred for diffusion transmission, conventional cameras and the like can be used, i.e. in the form of a light-sensitive element light-sensitive silver halide emulsion layer, contact with the developer before or after exposure and building up the image in or on a film carrier. the Developer composition preferably contains a high molecular weight ^, film-forming, viscosity-increasing, alkali-stable material or thickeners such as sodium carboxymethyl cellulose or hydroxyethyl cellulose. The developer mass is distributed in a known manner (U.S. Patent No. 2,543,181), it can break in one. borrowed containers be included. The two elements are only separated after the necessary exposure time.

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The image receiving layer preferably contains an or several silver precipitating agents or germs to build up of the silver image, e.g. metal sulfides and selenides, colloidal Metals, such as silver and gold, thiooxalates ^ lnd ThiOacetamide * These are preferably in a macroscopic manner coherent PiIm made up of sub-macroscopic agglomerates very small particles of a water-insoluble inorganic, preferably silicon-containing material, such as Embedded pebble airbirds (U.S. Patents 2,698,237, 2,698,245 and 2,774,667). The image receiving layer can also a dispersion of silver reducing or precipitating agents Be substances or initiators in the developer compound, so that the silver transfer image arises in this (US Pat. No. 2,662,822). Finally, in the developer mass a substance may be contained which'the hue of the Silver image more against blue-black; or neutral shifts (U.S. Patent 2,984,565).

A special feature of the photographic material according to the invention lies in the fact that negative transfer images are obtained with exposure indices by 1, 2 or more steps are greater than cie usually for a given silver halide emulsion required are. In the examples, the exposure is given as "f-numbers" Numbers represent a combination of the aperture and the Shutter speed, so that always the next F-number corresponds to the next possible combination of shutter speed and aperture; the higher the exposure index, the greater the f-number for a given luminance.

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F-number Locking device Aperture speed 1 1/25 f / 5.6 2 1/25 f / 8 3 1/25 f / 11 4th 1/25 f / 16 1/100 f / 8 VJl 1/25 f / 22 1/500 f / 5.6 6th 1/25 i / 32 1/500 f / 8 7th 1/25 f / 45 1/500 f / 11 8th 1/25 f / 45 1/500 f / 22 9 1/100 f / 45

At a luminance of e.g. about 18 cd / m, i.e. normal outdoor lighting, would need a diffusion transfer film with A.S.A. index 200 usually at Aperture 6 and a film with A.S.A. index 1600 at aperture 9. (In the examples, the exposures were made - unless otherwise stated - through a step wedge to a cold grille; a diffusion transfer film with an A.S.A. index of 200 would have to be exposed at aperture 2 under these conditions).

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In these examples the sodium thiosulphate was used as pentahydrate EFa ₂ SpO, .5HpQ, the atrium sulphite anhydrous and the potassium thiosulphate likewise anhydrous. The amount of silver per unit area was determined by X-ray fluorescence analysis and can be converted to silver halide by multiplying it by the ratio of the molecular weights.

Silver bromide is preferred as the silver halide emulsion or silver iodobromide, but it is also one Emulsion made of silver chloride with the usual sensitivity for copier papers (e.g. Kodak Azo and Kodak Kodabromide copier paper). The emulsions can arbitrary, e.g. panchromatically sensitized.

Generally speaking, you get better results with thin ones Developer layers, i.e. the development over one very small spacing takes place. The presence of potassium ions seems to speed up the transmission they will therefore often preferred * The concentrations of the various Reagents can vary, depending on the emulsion layer and other factors. Concentrations from 1-35 g / l i-Phenyl-5-mereaptotetrazole are particularly useful. the The concentration of silver halide solvent will vary with the concentration of the solubilizer, sodium thiosulfate solutions from 20-80 g / l are together with '1-Phenyi-5-mercaptotetrazole useful.

It is assumed that _t the transmitted complex is a complex of silver halide to the silver halide solvent is and- the solubilizer. Invisible transmission images are able to absorb ultraviolet light '. The usual complex of silver halide with an alkali metal thlo-

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ORIGINAL INSPECTED

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sulfate cannot absorb ultraviolet light, however i-Phenyl-5-mercaptotetrazole absorbs ultraviolet Light. Although it is possible that the i-phenyl-5-mercaptotetrazole to a certain extent also with the silver complex Image-receiving layer is transferred imagewise, it seems more likely that the i-phenyl-5-mercaptotetrazole part of a new complex with the silver halide solvent and the silver halide.

The "addition of a higher molecular weight thioether, such as alkyl polyoxyethylene thioether (»Cerfak 1500«) increases the sensitivity in some cases by 3 values.

(U.S. Patent 2,938,792).

The photographic material according to the invention can also be used to produce additives Color images obtained when the photosensitive *; Silver halide emulsion over an additive color grid exposed »the silver halide from the image areas is transferred to another layer and that in the image-free areas remaining silver halide is subjected to an overall exposure and developed; you get a positive one Silver image that corresponds to the image in the color grid. At a Another embodiment may be the transferred silver halide reduced to a dye image in the presence of a color developer and color coupler; the precipitated Silver can then be bleached out so that only the color image remains in the original image-receiving layer. In such an embodiment, the color coupler

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be non-diffusing and initially located in the image receiving layer are located; the same developer is used for both images. The developer oxidation product in the image areas is fixed, i.e. it cannot be over- * be worn as it is with the non-diffusible Coupler in the emulsion layer has reacted. One can provide in the emulsion layer such a coupler which provides a substantially colorless coupling product. The silver transfer image obtained in accordance with the present invention can also be used to produce a color image by the silver dye bleaching process.

Because of the remarkably high light sensitivity of the Photographic material according to the invention is particularly suitable as a recording material in poor lighting conditions, such as in X-ray photography, for recording light traces in der Wacht etc. Since an "overexposure" of the photographic material according to the invention in a simple manner completely or partially changes the type of the transfer image Conversely, information can be captured photographically over such a large range of exposure as if one were actually a continuous photometer would have.

In the development solution process \> ΐ ± τ & the finest grain exposed last and developed last, and the coarsest grain probably most likely exposed, developed and partially dissolved. In common positive silver transfer processes, the finest grain is dissolved first. Has a bead in the inventive photographic material even started to develop, it will either silver in ¹ situ reduced or dissolved completely.

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The developing solution method works in a wide temperature range and that between O and 38 O ⁰ in general with improved sensitometric values than conventional positive silver transfer process. This is probably due to the fact that the relative solubility, speed and developability are initially quite similar and this is also maintained with changes in temperature. It was found that the reproducibility with the photographic material according to the invention is at least equal to the usual silver transfer processes and thus the constant quality of the photographic material and image is guaranteed.

The silver halide in the non-image areas of the emulsion layer is in spite of the action of reagents believed to be photosensitive salts or Form complexes, still sensitive to light.

It should be noted that the invention does not "fix" or "stabilize" the silver halide in the non-image areas with the formation of a light-insensitive, relatively insoluble salt or complex. but the undeveloped and undissolved silver halide in the non-image areas of the silver halide emulsions remain sensitive to light.

This could not be foreseen, since it is known that developed silver halide emulsions "fix" or "stabilize" should be inactivated by inactivating undeveloped silver halide in situ is achieved by treating the developed but unfixed negative with sodium thiosulphate, potassium thiosulphate, Thiourea, etc. (U.S. Patent 2,614,927) or by Development with a developing agent such as 6-amino-4 ~

90 9 8 51/0987 - 29 -

r31 135

- 29 -

hydroxy-2-mercaptopyrimidine, 4

pyrimidine ^ (U.S. Patent 2,525,532). '·

The photographic material of the present invention for the development solution process is to be distinguished from a "photo -v solution" process (USA patents 3,155,506-7 and 3 155 514-9). Here the silver halide emulsion is treated with e.g. mercapto compounds before exposure and after exposure without developer substance subjected to the action of a silver halide solvent to dissolve the exposed silver halide. That Any remaining undissolved silver halide can then be exposed and reduced to silver. The one for that The exposure required by photo-solving techniques is much greater than it is applicable in cameras, too the sensitivity extremely low. The inventive However, photographic material has excellent Sensitivity, silver halide is only dissolved where. the initial development took place.

With the photographic material according to the invention, the development take place in a strongly alkaline medium, namely much more alkaline than required for the "photo-solution process" acidic fixing bath, e.g. I fixing soda.

1-Phenyl-5-mercaptotetrazole is already used in photo technology, e.g. as a toner or retarder (USA patent 2,699,393), namely mercaptotetrazoles, especially i-phenyl-5-mercaptotetrazole, as silver transfer image toner in amounts of 0.01 to 1 g / l in the developer, in contrast, according to the invention, substantially larger amounts of these mercapto compounds are required.

- 30 909851/0987

1A-31 135

- 30 Example 1

An Eastman Kodak Royal X Pan negative photographic material

ρ worth

(1.001 mg Ag / cm) was exposed at f-stop 6 and one Developer compound in a layer thickness of about 56 / rev between the exposed photo layer and a superficial one applied hydrolyzed cellulose acetate film. ~ -

The developer compound contained:

water

Hydroxyethyl cellulose sodium hydroxide

Sodium sulfite

Shark thiosulfate

Diethylamine

Ascorbic acid

4,6-diamino-ortho-cresol sodium sulfide solution (156 mg / cnr

Na ₂ S)

Lead and cadmium acetate solution

(100 cm? «Ο, 2.9 g lead acetate,

2.1 g cadmlum acetate) 0.34 cur

1-phenyl-5-mergaptotetrazole 0y03 g

9.1 CET 0.41 S. 0.26 S. 0.33 S. 0.14 S. 0.5 CDr 0.6 G 0.02 G 0.011 cm ⁵

After an exposure time of 3 minutes, the cellulose acetate film separated from the negative. The layer of developer compound on the cellulose acetate film then contained a negative silver transfer image.

- 31 909851/0987

- - 31 - ■■ '.. ■

You can use different photo layers and layer thicknesses of the developer compound, e.g. Eastman Kodak Super Panchro Press B-Negative 0.716 - 0.729 cm ² / Ag for aperture 5 "at 4-6yu, Eastman Kodak RS Pan-Negative for aperture 5 at 66 / u, Eastman Kodak Portrait Pan-Negative

0.877 mg cm / Ag for aperture 3 at 66 / u, Eastman Kodak

2 Super XX Panchromatic negative 0.758 mg / cm / Ag for Aperture 5 hei 66 / i, Ansco Versa Pan-Negative for aperture

2 3, Eastman Kodak Royal Ortho-Negative 0.73 ^ mg / cm / Ag for Aperture 6, 40 / rev, but with 0.07 g i-phenyl-5-mercaptotetrazole in the developer composition, Eastman Kodak "Commercial Film" 4-x5 negative 0.733 mg / cm / Ag, aperture 3, developer composition 60 / U with 0.09 g 1-phenyl-5-mercaptotetrazole,

/ ρ

DuPont T-508 X-ray negative 1.172 mg / cm / Ag, f-stop 5, • developer mass 50 / u, 0.07 g 1-phenyl-5 ^ mercaptotetrazole,

5 min, Eastman Kodak Gravure Copy-Negative 0.509 mg / cm / Ag, Aperture 4, developer mass 50 / U, 0.12 g i-phenyl-5-mercaptotetrazole, 4 min.

B ei s ρ i el

A lighted photographic material Ansco Super Hypan negative 0.603 mg / cm / Ag (aperture 5) was treated with a developer compound in a layer thickness of 60 Ai of the following composition:

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1A-31 135 - 32 -

water 124 cur Sodium sulfite VJl S. Sodium carboxymethyl cellulose 5.5 G Ascorbic acid 9 G 4,6-diamino-o-cresol 0.3 S. Diethylamine 7.5 cnr Sodium hydroxide 3.85 G Potassium thiosulfate
Sodium sulfide solution (156 mg / cur
Na ₂ S) 7.2
'0.177 G
cm?

Lead acetate-gadmium acetate solution
(100 cm3 H ₂ O, 2.9 g lead acetate,

2.1 g cadmium acetate) 5.25 cm ^

i-hienyl-5-mercaptotetrazole 0.38 g φ

One can do the following with equally good results Make variations: "high speed panchromatic" negative 0.107 - 0.12 mg / cm / Ag, f-stop 8 1/2, devolatilizer 38 / U an additional 0.1 g of potassium thiosulphate, developer compound without sodium hydroxide and diethylamine, but with 0.35 g potassium hydroxide, developer compound without sodium hydroxide, but with a diethylamine concentration of 1.6 cm., developer material without diethylamine.

i s ρ i e 1

"high speed panchromatic" silver halide negative photographic material (0.107-0.12 mg / cm ² / Ag), aperture 5, developer compound 66 / U with the following composition between negative and

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1A-31 135

superficially hydrolyzed gelulose acetate film

water 920 cm ^ Sodium carboxymethyl cellulose 38.9 g Sodium hydroxide 25.8 g Sodium sulfite. 33 g Potassium hydroxide 10 g Potassium thiosulfate 46 g Hydroquinone ' 10. g i-bhenyl-5-mercaptotetrazole 3 g Metol 30 g Diethylamine 50 cm ⁵

This system contained no syrup filler. After 4 minutes, the gelulose acetate film with the developer layer was separated from the developed negative. The developer layer, which was still wet, was completely transparent to the eye. She was taken quickly in a Vergrößerungaapparat, and still wet on common VergrößerungspapiW with a Wi-calibrate τ Irichtquölle copied. A good positive image was obtained if the copier paper was customarily developed. So there was öiü in the developer layer. un * H # «clearly visible, UV-opaque image of the transferred silver complex that looked like a negative» before *

In a modification of this process, the I developer layer was dried on the carrier and the transferred silver complex was precipitated with it. One received a visible one. Image in the form of a white precipitate · The _Λ ausgir- precipitated complex was relatively he lichtundurchläeaigi

909851/0907 "

1A-31 135 - 34 -

reflects and scatters the light, so that the image areas appear white in incident light and black in transmitted light. According to general appearance and usability the image thus obtained is a bubble image similar.

Another option is to use the negative separated cellulose acetate film with the wet developer layer quickly on top of an image receiving layer containing a silver precipitant * After some Seconds began to build up a silver transfer image, through the back of the transparent cellulose acetate film could be observed. After the appropriate image density had been reached, the image-receiving layer was peeled off. The duration of this second exposure varies, and results can be obtained in approximately 5-10 min.

B e P 1 έ 1 4

Between a bell el * tem "high speed" panchromatic Negitttv-l'nötöaaterial (0 £ t523f mg / cm ^ / Ag »aperture 6) and one Image-receiving element "Type 4? Polaroid Land Film" became developer compound in a bead of 56 / U following composition applied:

850

Hydrpa ^ ethyl cellulose 32.5 g

NatriTamaulfi | 53.3 g

Sodium thiosilicate 19.3 g

40.5 g

- 35 908851/0987

1A-31 135

· '- 35 - tolyhydroquinone 35.6 g

/ cm ^y

and 5 μ / cm ^{y of} 2-mercaptoethyl sulfide. After 2 minutes, the image-receiving element with the negative transfer image was separated from the negative.

It is also possible to use a developer composition containing 6 mg 2-Mercapto-5-furyl-1,3,4-oxadiazole with an exposure time of 1.5 min or 7 mg of 2-Hercapto-A-methyl-pyrimidine hydrochloride to be used with an exposure time of 5 minutes.

Example 5

A silver halide emulsion was prepared as follows: 60 cnr of a solution of 30 g of silver nitrate in 360 cm · 'of water of 60 cm was poured into a solution of 54- »6 g of ammonium bromide, 6.1 cm-' of a 15% strength potassium iodide solution, 4 -, 5 cur of a 28% ammonium hydroxide solution and 30 g of gelatin in 660 cm * water at 70 ° 0 and stirred in the remaining silver nitrate solution after 8 min. After 5 minutes, the first half of a solution of 60 g of silver nitrate in 360 cm * water of 60 ^° C. was added within 1 minute and after 10 minutes the second half was added within 1 minute. After 2 minutes the reaction mass was rapidly cooled below 20 °.

The emulsion was made with a 50 wt .-% ammonium sulfate solution precipitated and the precipitate washed out until the supernatant liquid has a conductivity of -500 / Uiss / cm. The washed precipitate became 33 g active Gelatin added, the gelatin dissolved and the precipitate melted at 35 ° C, the volume of the emulsion.

- 36 - ■ "· 9 0 9851/0987

1A-51 155 - 56 -

was set to 800 cm, the pH value to 6p and pAg value

ο 3

adjusted to 8.9, heated to 60 0 and 1 cnr of one Gold thiocyanate sensitizer (0.25 mg gold and 10 mg Ατητηonium thiοcyanat) added. The emulsion matured to its optimum Sensitivity in 95 min; thereafter the pAg value adjusted to 9j10 and the emulsion cooled. It contained silver and gelatin in a ratio of 1: 1, i.e. 66.2 mg / cnr Ag.

The coating was carried out with a solution of 5 S gelatin,

7. 7.

10 g emulsion, 40 cnr water and 0.25 cnr of a 25% strength Wetting agent solution (Triton X-100). It was mounted on cellulose acetate film support (245.84 cm long, 12.7 cm wide) at a speed of 504.8 cm / min. (remainder of the solution 15.5 g) This photographic material was then exposed at aperture 5 and developer compound in a layer thickness of 51 / "U- and a customary one on top Image receiving element "Type 47 Polaroid Land Film" applied. The developer compound contained:

water . 9.2 cm ⁵ Sodium carboxymethyl cellulose
(medium viscosity) 0.15 g Sodium carboxymethyl cellulose
(high viscosity) 0.26 g Sodium sulfite 0.55 g Sodium hydroxide 0.26 g Kai iumhydr oxi d 0.1 g i-phenyl-5-mercaptotetrazole 0.05 g Amidol 0.60 g Potassium thiosulfate 0.48 g Diethylamine 0.5 cnr ⁵

909851/0987

- 57 -

. . 1A-31 135

-.37 -.

After 4 minutes the image-receiving element was separated and washed the developer layer, there was a negative silver transfer image in the image-receiving element. - _

Example 6 .. ·

A fine-grained, photosensitive element for the

2 radiography (0.1932 mg / cm Ag) was performed at aperture 4 exposed and between this negative and a superficially hydrolyzed Oellulose acetate IOlie as Carrier developer compound_ 46 applied too much.

water

Sodium carboxymethyl cellulose Ascoric acid

4,6-diamono-o-cresol V diethylamine

Sodium hydroxide

Ealium Thiosulfate

Sodium sulfide solution (156 mg / cur

Na ₂ S)

Lead acetate / cadmium acetate solution (100 cm ^ H ₂ O, 2.9 g lead acetate; 2.1 g cadmium acetate) . ".

Sodium sulfite
i-phenyl - ^ - mercaptotetrazsol

920 cm 38.9 S. 60 S. 2 S. 50 cm 25.8 S. 42 G _ "3

35, 5 cm 33 G 2, 2:

- 38 - ^l

909851/0987

1A-31 135 '- 38 -

After 3 minutes, the carrier was separated from the negative in the dark, in the developer layer on the hydrolyzed surface of the cellulose acetate film was negative Sirber transmission image.

The separated negative was washed in the dark, exposed again and the one formed in this way Picture in the tray with "Kodak Dektol-Entwiekler" (undiluted) developed what could be followed visually. The maximum density was reached in about 1-2 minutes. It was now placed in a fast-working, acidic fixer, there was hardening but no real fixation. That ■ positive silver image showed when looking through D 1.80 and

Example 7

A silver halide emulsion with precipitating, colloidal gold was applied to barytaised paper, exposed with aperture 2 and between this negative and a superficially hydrolyzed cellulose acetate film applied as a carrier developer compound 26yU.

Water 9.1

Ifodium carboxymethyl cellulose 0.39 g

Sodium hydroxide 0.257 g

Potassium thiosulfate 0.28 g

Sodium sulfite 0.33 g

Ascorbic acid 0.6 g

4,6-DiamirucH-o-cresol 0.02 g

. - 39 -

909851/0987

1Δ-3.1 135

3 diethylamine 0.5 cm

i-phenyl-5-mercaptOtetrazole 0.022 g

After 5 minutes the photosensitive element was with separated from the latent image in the dark and fixed for 3 min. A very dense negative silver image D 3.05 and D was obtained. 0.4- (base blackening 0.25). In cLen

HloLX III J. Xl ^.

No silver deposition occurred in non-image areas, despite the fact that a precipitating agent was present in the emulsion layer. A comparative emulsion without silberausfällendes agent yielded under the same conditions with a negative image D _{Λ Ό,} 85 and D _n. 0.33 (base

HLcL) C ium

ium

Blackening = 0.25) and therefore much lower sensitivity »

Example 8

Five strips of highly sensitive, panchromatic

- 2 negative photographic material (0.1533 mg / cm / Ag) were taken from the Apertures 3, 5, 7, 9 and 11 exposed the latent image coated with developer compound 4-6> u and with a Image receiving element covered. 1 1 developer compound contained:,

Sodium carboxymethyl cellulose

(medium viscosity) ■ ■ ... 13.9 g

Sodium carboxymethyl cellulose

(highly viscous) 25 g

Potassium thiosulphate 48 g

Sodium sulfite 33 g

Potassium hydroxide 10 g

90985 1/0987

BATH ORIGINAL

1A-31 135

- 40-

Metol 30th G Hydroquinone 10 G Diethylamine 50 cm Sodium hydroxide 25th , 8 g 1-phenyl-5-mercaptotetrazole 3 δ

After 3-5 minutes, the image-receiving element was separated from the negative and the blackening curves (log it) versus ^ for;} each silver transfer image were determined (FIG. 1). The density at trananission, the type of image formation and the exposure indices of the transfer images obtained at the various f-stops are listed in the following table

- 41 -

909851/0987

Tabel

1A-31 135

F-number

3 5 7 9 11

Image Type Transmission Density Exposure Index for D_ _ D "4 ^ positive negative

image

Max

2.49 2.50 2.43 2.48 2.55

0.33 1 500 23 000 0.37 .1 550 16 000 0.35 6OQ 32 000 0.35 100 30th 000 0.58 - · -

The indices were determined 0.5 units over D _min in transmission. What is particularly striking is the similarity of the blackening curves, the maximum blackening, regardless of whether the transfer image is positive or negative, and the noticeably greater sensitivity for a negative image than for a positive image.

- 42 -

909 851/0987

1A-31 135 - 42 -

The image-receiving element used here was made as follows ;

Gold was on a wire in vacuum (about 10 "mm Hg) 50 g triacetate cellulose -]? Curls evaporated; in fact 2.6 wt .-%, 11 g of this product was in 109 cm of ethyl acetate et at, 36 cnr methanol and 3 cur water dissolved and dissolved Baryta paper 9 / U heavily coated. The cellulose acetate layer was superficially hydrolyzed to cellulose (US Pat. No. 3,078,178), about half that Layer thickness

Example 9

A highly sensitive panchromatic i-negative photographic material (0.1533 mg / cm / Ag) was exposed at aperture 8 and between this and an image receiving element "Type 47 Polaroid! Found film "Development Compound 56 / U heavily applied: ι

Water Ί 9.2 cm ⁵ Ifatriumcarbo ^^ piethylceilialose 0.39 g Sodium sulf itj. 0.64 g Sodium hydroxide 0.49 g üioitthydrochiiion 0.36 g Hatriumthiosi | lfa> 0.23 S 5-ilfitroinda! S <i »l 0.05 g

lfii0lJ. 2 min wijtrdf separated the image receiving element, it contained a negative ^ silver transfer image

; Jk: -Ί ■ ; . ■ ■ ■; - .. ■■. "■. 43 - -

«Ί
ι r

1A-31 135

- 4-3 -

Example 10

A fine grain silver halide X-ray photographic material low sensitivity (0.1934 mg / cm / Ag) through, a 1.0 neutral density filter 1 see with a 7.5 W lamp exposed at a distance of 1.2 m and treated further according to Example 1, but one 66 / U thick developer layer applied. To. 3 min this one a silver transfer image with negative and positive kind,

If the developer was applied 0.2 seconds before exposure, a very similar silver · Transfer image, however, with a slightly lower degree of blackening.

- ■ "■ - ■ *". ■ '

Eg game 11

The photographic material from Example 10 was exposed to 1/25 second (f / 4.5) and between this negative and a superficial, hydrolyzed gelulose acetate film, developer composition 46 / U applied:

water 9.0 cm ⁵ Sodium carboxym e thylc ellulose 0.4 g Sodium sulfite 0.33 g Potassium thiosulfate 0.14 g Diethyl amine 0.5 cifl ^ ' H, H-diethyl-hydroxylamine 0.7 cnr ⁵ Sodium hydroxide 0.26g Sodium sulfide solution <156 mg / cm '
Na ₂ S) _; 0.012 cm ⁵

■. - 44 -

9 0 9Ä51 / 0087

1A-31 135

- 44 -

Lead acetate-oadmium acetate solution (100 cm ^ HgO, 2.9 g

Lead acetate, 2.1 g cadmium acetate 0.36 cm i-phenyl-5-mercaptotetrazole 0.025 g

After 3 minutes, the cellulose sheet with the image-bearing Developer layer peeled off.

Example 12 !.

The measures of Example 11 were taken with a slightly

another 86 yu. strong developer layer repeated »

Water ■ 9.0 cm ^

Sodium carboxymethyl cellulose 0.4 g

Sodium sulfite 0.33 g

"Potassium thiosulfate 0.14 g

2, ö-Diniethoxy - ^ - amino-

phenol hydrochloride 0.08 g

Ascorbic acid 0.6g

Methylamine 0.42 cm

Sodium hydroxide 0.26 g

Sodium sulfide solution (156 mg / cur 0.012 cm ^

Na ₂ S)

Lead acetate / oadmium acetate solution (100 cm3 H ₂ O, 2.9 g lead acetate, 2.1 "g oadmium acetate). 0.36 cm- ^

2-thio-6-azauracil. 0.05 S

A negative silver transfer image was obtained in the developer layer. ■.

909851/0987

1A-31 135

B e i s ρ ie 1 13

The measures of Example 12 ^ were carried out with Kodak Azo F / 2 copy paper, Exposure 0.2 sec, development 5 min xdLederholt. A negative transfer image was obtained in the Developer layer. ....--.

With a Kodak kodabromide I '^ copy paper you need for f / 4.5 an exposure time of 1/10 sec.

B e i s ρ i e 1

14th

A highly sensitive, panchromatic negative photographic material

high speed (0.1554 mg / cm Ag), an image receiving element Containing "Type 47 Polaroid Land Film" and a developer composition with a thickness of 46yu

water

Sodium carboxymethyl cellulose.

Ealium hydroxide liatric sulfite Sodium hydroxide diethylamine potassium thiosulfate 2,4-diaminophenol dihydrochloride

9.0 ecm 0.4 g 0.1 g 0.33 g 0.26 g 0.5 cc x 1.4 g
0.6g ",

to create a negative image D "__ 1.05,

XUcL-Λ.

D. 0.05 applied after a development time of 4 minutes in the image-receiving element, that of the superficial silver and remaining developer is freed. It was found that the higher the potassium thiosulfate concentration

9 098 51/098 7

- 46 -

15t7986

1A-31 135

- 46 -

negative transmission images received in 20 see However, the density of the transfer image is less. . '

Example 15

A medium to high sensitivity orthochromatic

■ ■ 2 negative photographic material with paper backing (0.1958 mg / cm / Ag) tmd containing a developer layer 63 / U "

water

Hydroxyethyl cellulose Potassium thiosulfate

Sodium sulfite

Ascorbic acid

4,6-diamino-o-cresol diethylamine

Sodium hydroxide

Sodium sulfide solution (156 mg / cnr

91.0 ecm

3.9 g

2.8 g

3.3 g

6.0 g

0.2 g

5.0 ecm

2.5 g 0.118 ecm

Lead acetate-cadmium acetate solution

(2.9 g lead acetate, 2.1 g oadmium acetate,

100 ecm H ₂ O) 3.55 ecm

i-phenyl-5-m.ercaptotetrazole

0.22 g

on a superficially hydrolyzed cellulose acetate, films were developed for 10 minutes after exposure (aperture 3). The blackening curve of the negative silver transfer image in the developer layer at (transmission is in Fig. 2 curve B reproduced. If a developer composition without i-phenyl-5-mereäpto-tetrazole is used, a

- 47 90985 770987

1A-31 135 ■ .- ■ ■

- 4-7 -

positive silver transfer image (curve A) after 1 min Exposure time. The negatives of all of these attempts xtfurden fixed in the dark and the blackening curves (Reflection) determined: Fig. 2, curve D after 10th min with i-rienyl-5-mereaptotetrazQl and curve C after 1 min without i-phenyl-5-meTcaptotetrazole. In curve C. Background density 0.24- "taken into account. When developing with i-Ph.enyl-5-mercaptotetrazole was obtained in 1 min pale: negative transmission image. That fixed, from the A negative image developed in areas of the negative Curve E. The similarity including the maximum densities of the curves - especially the curves - is remarkable C and D as well as curves B and A.

Example 16

The sheet photographic material of Example 10 (aperture 4x) and Non-viscous developer containing

Water 180 ecm

Has riumhyclr oxide 5.2 g

Potassium thiosulfate., 7 »0 g

Calcium sulfite 6.6 g

Ascorbic acid 12g

2,4-biamino-o-cresol 0.4 g

Diethylamine - ·· ... ^, _{0 CCI} ^

i-Hienyl-4-mercapto.tetrazole 0.4- g ■■■ ·. ".

gave after 3 min of development and washing and again total exposure and development - 2 - 3 min in the tray with Kodak Dektol developer (undiluted)

.. ·. -4B 9098517098 ^

1A-31 135-48 "blue positive image in the emulsion layer.

If, as a modification to this, the exposed photographic material is 3 min after immersion in the liquid developer subjected to a total exposure and another 2-3 min in that Leaving the EntxcLckler in place, a good positive image was obtained.

Example 17 "

The photographic material of Example 14- (aperture 7) uncL one Containing developer layer, 56 / U

Water 100 ecm

Sodium carboxymethyl ceiru.lose 5? 0 g

Sodium hydroxide. "15jO g

Uracil 11.25 g ammonium hydroxide solution 29.4 yg 3.5 ecm

N, N-diethy! Hydroxylamine 7) 5 ecm

i-phenyl-5-mercaptoteträzöl 0.2 g

resulted in 4-7 Polaroid Land Fi-Im in an image receiving element a negative transfer image after 4 · min.

With exposure above f / 6 and a development time a negative transfer image of somewhat lower density was obtained from 3 Elin. -

Example 18

A roll film (US Pat. No. 2,579,587) from a high-

- 49 _

909851/0987

1A-31 135 -

- - 49 - ■ ". ■

sensitive, panchromatic negative photographic material (0.1533 mg / cm ² , Ag), an image receiving element (47 Polaroid Land I'llm) and a bag with the developer composition of Example 5 in a "Polaroid Land Camera", model 150, ■ exposed at light value 10 and aperture 1 in a room only with incidence of daylight and after about 1 minute the image-receiving element separated from the negative material, it contained a negative silver transfer image of good quality.

If the light is now exposed again with artificial room lighting and the same light value, a positive silver transfer image was obtained after 1 min in the image receiving element.

However, for comparison with light value 10 (aperture 1) it was without Room lighting with the same photographic material (equivalent ASA exposure index 3200) was obtained after 10 see a positive silver transfer image. Repeated If you do this comparison experiment with room lighting, the correct light value is 13 at aperture 4. In this way can already be used for photographic materials with an equivalent ASA exposure index of ^ only 400 a positive transfer ■ image and obtained a negative transfer image with an equivalent ASA exposure index of 3200.

B e i s ρ i e 1 19

Copy paper from Example 13 was exposed for 1/10 sec and 89 / U developer compound between the paper and a Baryta paper carrier distributed. ·

■ · - 50—

9 0 9851/0987

1A-31 135

- 50 -

Water '9 ₅ 1 cm

Sodium carboxymethyl cellulose 0.4 g

Ascorbic acid 0.6 g

Sodium sulfite 0.6 g

Sodium hydroxide 0.26 g

Sodium sulfide solution (156 mg / ccm _Q

Lead acetate / cadmium acetate solution. 0.34 ccia (2.9 S lead acetate, 2.1 g cadmium acetate, 100 ecm H ₂ O

After 3 minutes, the carrier was cleaned with the decoiler peeled off showing a negative silver transfer image Template. In this mass is used as a silver halide solvent only sodium sulphate and ascorbin as a nutritional agent contain acid.

PATENT CLAIMS

909851/0987

Claims (10)

3? a t e η t a n s ρ r ü c h e 1. Process for the "production of photographic images, in particular by the silver salt diffusion transfer process, with a photosensitive silver halide emulsion layer which is exposed imagewise and the latent image is developed with an aqueous alkaline developer composition containing a silver halide developer substance and at least one complexing agent for silver halide , -due \ ge Ic e η η ζ eic h n.-et, that the concentration of the complexing agents in the developer composition is set so that an image-wise resolution of the silver halide complex ^{1 is} only possible in the exposed areas in which the development has already started, takes place and, if necessary, transfers the silver halide complex to an image-receiving layer ... ..-: ■■■; .- ■ 2. The method according to claim 1, characterized in that that one precipitates the image silver from the complex by drying the image receiving layer. 3. The method according to claim 1, characterized in that g e k e η. η drawing η e t that one contains an image receiving layer a silver precipitating agent. - 2 - 9098 5 1/098 B, 1A-31 135 4. The method according to claim 1 or 2, characterized in that a developer composition, containing a silver precipitating agent. 5. Method according to claim 1, characterized in that g e k e η η ζ Ei chn et that one uses an emulsion layer which before exposure a silver precipitating agent and the silver halide complex essentially in situ to produce a negative silver image reduced in the emulsion layer. 6. The method according to claim 1, characterized-. ge: ke η η ζ ei chn et that one brings together a second, light-sensitive layer with the moist layer containing the imagewise distribution of the diffusible complex, which absorbs UV radiation, to reduce the complex to silver and the second layer with UV radiation exposed over the image-bearing layer, as a result of which a developable image ^{J is} built up in the second layer, which image is developed into a positive image in the usual way. 7. The method according to claim t, characterized in that the dissolved silver halide complex removed from the emulsion layer, exposed without prior fixation and the resulting build up Developed a positive image. 8. The method according to claim .1, characterized in that the dissolved silver halide complex removed from the emulsion layer and this fixed to a negative silver image. '- 3 9098 5 1/0987 ' - \ - 1A-31 135 9. Procedure according to. Claim 1 to 8, characterized in that one is used as complex-forming Medium used sodium or potassium thiosulfate 10. The method according to claim 1 to 8, characterized in that that a substance with the grouping is used as a complex-forming agent SH SH. .. SH -M = QE-, N = CJ-O- or -N = GS- used, especially 4-methyl-2-mercapto-oxazoline or i-phenyl-5-mercaptotetrazole, the latter, in the developer, preferably in a concentration of at least 1 g / l. 9098 5 1/0 98 7