DE1155334B - Silver salt diffusion transfer process and material for it - Google Patents

Description

According to the well-known halogen silver diffusion transfer process, the principle of which is in the Belgian Patent specification 441852, its additional patents 444 784 and 444 785 and in the German patent specification 887,733, a photosensitive halogen silver emulsion layer becomes image-wise exposed and in the presence of a developer and a solvent for the halogen silver pressed against a specially prepared receiving layer for this purpose. The exposed image ίο parts are developed and then no longer subjected to any further changes. The unexposed Parts of the halogen silver are dissolved by the solvent for the halogen silver, which is either located in the receiving layer or in the developer, by diffusion onto the pressed receiving layer transferred and there converted into metallic silver by development. This implementation takes place with the help of the development nuclei located in the receiving layer, which consist of finely divided metal or Look at metal sulfide. When the emulsion layer and the receiving layer are separated, one thus obtains the latter a picture.

In order to achieve a uniform diffusion of the silver salts, halide silver emulsion layer and Receiving layer are in close contact for a certain period of time. If now both layers hardened or Containing unhardened gelatin, the mutual adhesion is too strong for easy separation of the To grant layers after a prolonged contact time. One has tried to overcome this difficulty by doing this to avoid replacing the gelatin with other binders.

Thus, according to the German patent specification 869 008, the separation of the halogen silver emulsion layer and the receiving layer is facilitated when the gelatin in at least one of the layers mentioned wholly or is partially replaced by other layer-forming substances, e.g. B. by cellulose derivatives, polyamides, Polyesters, polyvinyl alcohols, polyvinyl acetates, partially hydrolyzed polyvinyl acetates, polyvinyl acetals or other synthetic or natural resins.

According to British Patent 748,892, the halide silver emulsion layer and the image receiving layer are said to be Strength to be incorporated.

From British patent specification 814 154 it is also known that the separation of halide silver emulsion layer and image-receiving layer made even after practically complete drying can be added if starch ether or galactomannan is added to at least one of these two layers is.

Silver salt diffusion transfer process
and material therefor

Applicant:

Gevaert Photo-Products NV,
Mortsel, Antwerp (Belgium)

Representative: Dr. W. Muller-Bore

and Dipl.-Ing. H. Gralfs, patent attorneys,

Braunschweig, Am Bürgerpark 8

Claimed priority:
Netherlands of October 20, 1960 (no.257 057)

Dr.-Chem. Louis Maria de Haes, Edegem (Belgium), has been named as the inventor

Another method, the separation of the halide silver emulsion layer to facilitate from the image receiving layer is that a thin surface layer applied to the halide silver emulsion layer and / or to the image receiving layer will. According to German Patent 1,055,953, starch or starch derivatives can be used for this purpose use.

If you have a non-sensitive material and a Image receiving material is used, one of which has such an auxiliary surface layer to facilitate separation contains, it is often observed that the transfer images obtained are likely because of the effect of the roller pressure in the developing device on the insufficiently hard and too easily swelling Auxiliary layers are out of focus. This poor image sharpness occurs very often when the halogen silver emulsion layer and the image receiving layers are separated from one another after only a short contact time.

The above difficulties are overcome with the aid of the materials and methods of the invention or decreased.

It has now been found that by halogen silver diffusion transfer Sharp images are produced from an exposed photosensitive material onto a non-photosensitive material if the light-sensitive and / or light-insensitive material carries a surface layer that is entirely or for the Part of at least one water-insoluble metal

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alginate. Even if the silver halide emulsion layer and the image receiving layer only left in contact with each other for a short time after the silver complex diffusion transfer, Sharp images can be produced if one of the materials contacted is in the surface a water-insoluble metal alginate is present.

When using preferred materials according to the invention, as described below,

A material that is insensitive to borrowing according to the invention contains a layer, after which complexed halogen silver from the unexposed areas one imagewise

agent for the halogen silver and a developer together stand in touch. It also contains one or more substances that help develop

rial uses a water-insoluble salt of alginic acid, although - as already mentioned - it is possible to add such a salt only to the light-sensitive material, z. B. the halogen silver emulsion layer or 5 a layer applied thereon. In the description, particular emphasis is placed on the production of an image receiving material according to the invention described.

An image receiving material for use in

can be achieved in such short contact times using a halogen silver diffusion transfer process Transfer images achieve that it is possible two, as is known per se, a carrier, e.g. B. or several prints from one and the same arbitrary paper, and a colloid layer, usually a getete to obtain photosensitive sheet. latin layer, after which the halogen silver

The materials tend even after a long period from the unexposed areas of the photosensitive Contact time or even after complete drying 15 material overdiffused. When making a in a warm or cold state, the image receiving material of this type according to the invention does not to stick together strongly, so that they can look for a thin layer on the colloid layer when to separate them from one another, to tear them apart. formed by adding a water-soluble salt The invention encompasses both photosensitive solutions containing alginic acid, as well as light-insensitive materials, which can be used in any layer a water-soluble use the procedure described above. Incorporate salt, which hardens the metal alginate layer,

z. The support, the colloid layer or said surface layer solution, but preferably one layer immediately below, d. H. the KoI

exposed material can diffuse if 25 loid layer or another layer on the KoI-these Materials in the presence of a solvent layer, before applying the water-soluble

Alginate salt. Hardening takes place soon after the surface layer has been applied.

The amounts of added water-soluble melamine of the over-diffusing metal salts as described above may vary within wide limits, promote halogen silver to silver, and one or more water-insoluble liters of layer-forming solution are selected in or on, but preferably between 5 and 20 g per this layer. These metal-metal alginates. A photosensitive salt according to the invention can also be incorporated into the alginate salt layer itself, which contains a material containing a halogen silver emulsion. In any case, the concentration layer, into which one or more water-insoluble tration of the metal salts in the layer-forming salts of alginic acid have been incorporated, or is solution such that the viscosity increase of this is provided with a layer consisting of one or more solutions does not prevent the shedding,
reren such water-insoluble salts consists or the necessary adhesion of the water-insoluble

this contains. Metal alginate layer on an underlying

One can produce material according to the invention, 40 layer is, as said above, greatly improved if by adding a hardener for gelatin, e.g. B. In layers of the material a water-soluble algin-formaldehyde or glyoxal is incorporated. One acid salt and a water-soluble salt, which such substance hardens the underlying gelatineches is chosen so that by reaction between the layer superficial by diffusion. This adhesion the water-soluble salts in situ a water-insoluble 45 is also noticeably improved if the alginate Alginic acid salt is formed. layer at a relatively high temperature,

In general, the molecular weights vary between 60 and 90 ° C, is applied, of water-soluble alginic acid salts for the preparation The use of a picture according to the invention

Development of a material according to the invention between the receiving material and / or light-sensitive Ma-18 000 and 200 000. Preferably used water- 5 ° terials leads to a substantial improvement in the soluble alginic acid salts are z. B. sodium alginate, halogen silver diffusion transfer process. Man Potassium alginate, ammonium alginate, magnesium alginate have a contact time of only 10 seconds. and triethanolamine ginate. When these salts achieved as drawn transfer images, and this he layered can be applied, such a layer enables the production of two or more abauss aqueous alginate solutions with a concentration of 55 draws from one and the same exposed light sensor about 5 to 60 g per liter of casting composition-sensitive sheet. A quick bath can now be formed. These quantities, however, are not the development required for carrying out the exposed if critical and are allowed to go through the developing device with a Gezen outside of this limit if so desired. speed of 7.5 cm / sec. allows with a

The following are examples of metals whose water-fast separation from exposed material and Soluble salts are very suitable to couple with an image receiving material, so that the diffusion water soluble Alginic acid salt a water-insoluble transfer process as a whole considerably accelerates compound to form: calcium, strontium, barium, nigt. For the treatment of photosensitive cerium, Uranium, titanium, chromium, manganese, iron, cobalt, borrowed material with the developer liquid Nickel, copper, zinc, silver, cadmium, mercury, 65 contact with the image receiving material be aluminum, Thallium and lead. required time can be reduced to 2 seconds per centimeter when performing a material length according to the invention in the direction of movement Procedure will preferably be in the image receiving material. After pressing the two together

Materials can be separated from each other after just 10 seconds. The developing temperature is preferably chosen between 18 and 24 ° C. A rapid development device is in the British patent 858,323. The inventive method is after well-known methods of halogen silver diffusion transfer and with the corresponding Materials carried out as in "Progress in Photography", 1955-1958, pp. 24 to 36, and the ones cited there Patent literature is described.

Any halogen silver emulsion is suitable for carrying out the process according to the invention exposed silver salt developed sufficiently quickly during the diffusion transfer process and their unexposed silver salt is also complexed sufficiently quickly. Chlorine silver emulsions are preferably used for this purpose used which may contain certain amounts of silver bromide or iodide or which contain certain ingredients to achieve the desired Emulsion characteristics may be added. Examples of suitable halogen silver emulsions are described in French patent 1140,526.

The image receiving layer can either consist only of a support or of a support and a water-permeable colloid layer cast on this support, the development nuclei for containing halogen silver.

Development nuclei are suitable for producing the silver-containing image in the image-receiving layer the sulfides, selenides, polysulfides, polyselenides, thiourea, mercaptans, stannous halides, heavy metals or their salts and veiled halosilver. Sulphides of heavy metals, such as antimony, Bismuth, cadmium, cobalt, lead, nickel and silver are also very suitable. Lead sulfide and zinc sulfide as well as their complexed salts alone or mixed with thioacetamide, dithiobiuret and dithiooxamide are particularly interesting. The heavy metals are silver, gold, platinum, palladium and mercury, preferably in colloidal form. Of these, the precious metals are the most effective.

These development nuclei can either be incorporated into the carrier material itself or from it Solutions or dispersions of such development nuclei in a colloidal medium, such as gelatin, immediately poured onto a suitable carrier such as paper.

In order to remedy the roll-up of the gelatin-containing image receiving material, as is generally known The coating composition for the image receiving layer is a polyhydric alcohol such as glycerine or sorbitol, added.

The composition of the developer solution for the halogen silver corresponds to that of the usual developer solutions for the halogen silver diffusion transfer: it contains the necessary ingredients for the Development of the exposed silver halide, such as hydroquinone and 1-phenyl-3-pyrazolidone, and optionally a solvent for the undeveloped silver halide such as sodium thiosulfate, sodium thiocyanate or ammonia. However, the solvent for the silver halide can be used as well Image receiving material be incorporated.

More information about the composition of the halogen silver emulsion layers and about the image receiving material, the baths and the exposure and development equipment can be found in the above-cited report in "Progress in Photography", in those mentioned there Patents and in British patent specification 858 323.

The following examples serve to illustrate the invention without restricting it in any way.

example 1

A paper support of 90 g / m ^{2 is provided} with a receiving layer composed of a 40 ° C. suspension of the following composition:

¹ S of water 675 cm ³

Gelatin 68 g

0, l% aqueous suspension of

colloidal silver 25 cm ³

Sodium thiosulfate 122 g

Sorbitol 100 g

Strontium chloride 10 g

This suspension is poured in such a way that 1 1 ^{covers 40 m 2 of} paper. After drying, a second layer of a 60 ° C solution of the following composition is applied to this layer:

Ammonium alginate 25 g

Water 965 cm ³

40% aqueous formaldehyde 10 cm ³

This solution is applied in such a way that 11 covers ^{50 m a.} Then you dry this layer. The image receiving material thus obtained is placed on the silver halide emulsion layer of an imagewise exposed light-sensitive material which has been prepared according to Example 3 of French Patent 1140,526. Both materials are then passed through a developer solution of the following composition at such a rate that each part of the material is wetted for 2 seconds:

Sodium hydroxide 11 g

Sodium sulfite (anhydrous) 100 g

Potassium bromide 1.5 g

Hydroquinone 9 g

1-phenyl-3-pyrazolidone 1.5 g

Water up to 1000 cm ³

Then pressing is carried out in a developing device, as described in British patent specification 858 323 is described, the image-receiving layer and the photosensitive layer together. After 10 seconds the image-receiving material and the light-sensitive material are separated from each other. You get an easily legible image of the original in the image receiving layer.

Example 2

You can achieve the same favorable results as in Example 1 if you are in the suspension that example replaced the strontium chloride with calcium chloride.

Claims (1)

7 8 Example 3 This solution is poured in such a way that 1 1 ._,. ,. ,,. ,. _n . . .. 17 m ^{2 of} photosensitive material covered. A transparent paper carrier is provided _{. An image receiving material is brought to} ^F which corresponds to the im of 60 g / m * with a receiving _{layer made of emer ßei M 1} , but none 4O ⁰ C warm suspension contains the following co- ₅ auxiliary layer, which after treatment the separating settlement. tion of the photosensitive material facilitated with an imagewise exposed gelatin chlorosilver layer ^Water 6S5 cm ^ of the _{above-described} highly sensitive material Gelatin 68 gj _n touch and then treats both materials 0.1% aqueous suspension of to as described in Example 1. After a contact colloidal silver 25 cm ³ time of 10 seconds, an easily legible one is obtained Sodium thiosulphate 122 g copy of the original. Sorbitol 100g Example 6 This suspension is applied in such a way that an image-wise exposed light is covered with 11 40 m ^{2 of} paper. After drying, sensitive material according to example 5 and a picture on top of it pours a second layer of a 60 ° C receiving material according to example 1 and carries out the de-warming solution of the following composition: winding and diffusion transfer as in example 1. After a contact time of 10 seconds Ammonium alginate 2 g ₂₀ den, the two materials can be easily separated Separate water 290 cm ^{3 from} each other. You get a legible copy of the 40% aqueous formaldehyde 10 cm ³ template. Strontium chloride 0.2 ^g of di ^{kaBn ese Bei ie} P l ^e migrate by the light-insensitive and the light-sensitive This solution is cast in such a way that one can use 25 material as soon as the latent 1117 m ^{2 of} paper covered. Then the image is dried in the light-sensitive material from the layer. After further treatment, this image separates and while the materials are still wet receiving material as in Example 1 is obtained, in a second or further light-insensitive positive image of the original. borrowed material by diffusion transfer from the 30 exposed photosensitive material one or more Example 4 _{eral W} generated ei _tere images. A paper support of 90 g / m ^{2 is} provided a receiving layer as described in Example 1. Patent claims: After drying, it is poured onto this from a 60 ° C. 1st process for producing images in warm solution of the following composition a 35 a non-photosensitive image receiving second layer: material through halogen silver diffusion transfer generation from an exposed photosensitive Ammonium alginate 60 g material, characterized in that material-water 930 cm ³ rials are used, in which one or 400 / o aqueous formaldehyde 10 cm »* ° both surfaces, which during the transfer are in contact with each other, from one or This solution is applied to the carrier with several water-insoluble metal alginates on that 11 covered 50 m ^{2 of} paper. Then stand or contain them, you dry this layer. _A ² method according to claim 1 using This image-receiving material is combined with a non-light-sensitive material with an image-wise exposed photosensitive ^em ^ ^T ™ fl 'T% ^ f ", the germs Material through a processing solution, as in the examples f ^> ^^ the Entwiddung of after this game 1 described. The two halogen overdiffusing layers are increased Adhesive materials from the developing 5 ^llbe 5 ^fordem ' ¹ ^ a surface layer there- and dries them under heat. Closing 5 ° characterized in that a surface Lich one separates both materials from each other. Man ^sclucht ™ f ^e ! / F ^! , ^ ^ un ^m receives a positive copy of the original. Contains water-insoluble metal algmates. 3. Material with an appropriate carrier, e.g. B. Example 5 Paper, for the method of claim 1, which 55 a layer, possibly a colloid layer, It provides a barytierten paper support of stops, can diffuse an image-wise exposed lichtempfind-10 g strontium chloride per liter gießklare emulsion ü _c hen material into the silver halide from the unexposed 90 g / m ² with a gelatin silver halide emulsion, the authorities if contains. This emulsion is cast in such a way that these materials are in contact with one another in the presence of a solution after drying 1.3 g of chlorine _silver per square meter 6o by means for the halide of silver and a developer, and the emulsion layer is cast on one or more substances , Top layer from a solution of the following composition, which the development of the overdiffusing settlement: promote halogen silver to silver, such as Ag or. . _t . "65 metal sulfide nuclei, characterized in that ammonium algmat 6 g there is one or more _{in or on this layer} ^{Water contains} 984 cm ^{3 of} water-insoluble metal alginates. 40% aqueous formaldehyde 10 cm ³ 4. Material according to claim 3, characterized in that shows that the colloid layer consists of gelatin. 5. Material according to claim 4, characterized in that the gelatin layer or on this applied layer contains a hardening agent for gelatin. 6. Material according to one of claims 3 to 5, characterized in that the colloid layer contains a metal sulfide. 7. Material according to one of claims 3 to 6, characterized in that it is a water-insoluble Contains metal alginate, which at least partly consists of the potassium salt or the strontium salt of alginic acid. 8. Material according to one of claims 3 to 7, characterized in that it is a water-insoluble Contains metal alginate, which is produced by the reaction of a water-soluble metal salt with a water soluble salt of alginic acid has been formed in situ. 9. Material according to claim 8, characterized in that it contains a water-insoluble salt, that by incorporating calcium chloride and / or strontium chloride together with ammonium alginate has been formed in this sheet material. 10. A material for the method according to claim 1, which comprises a photosensitive halide silver emulsion layer , characterized in that this halogen superemulsion layer contains a water-insoluble alginic acid salt or is provided with a layer consisting of such is or contains water-insoluble salt. 11. Material according to claim 10, characterized in that that it contains calcium alginate or strontium alginate as a water-insoluble salt. 12. Material according to any one of claims 10 and 11, characterized in that there is a Contains water-insoluble salt, which is produced by reaction of a water-soluble metal salt with a water-soluble alginic acid salt has been formed in situ. 13. Material according to claim 12, characterized in that it is a water-insoluble salt contains, by incorporation in this sheet material of calcium chloride and / or strontium chloride formed together with ammonium alginate. Considered publications:
German publication No. 1055 953. © 309 690/229 9.63