DE1118007B - Photographic silver complex diffusion transfer process - Google Patents

Description

The invention relates to a silver complex diffusion transfer photographic process for manufacture several prints from the same negative.

According to the general principle of the diffusion transfer process, as it is in the German patent specification 764 572, in the Belgian patent specification 444 784 and in "Photography, its materials and processes" by C. B. Neblette, 5th Edition, pp. 234-244, is an imagewise exposed photographic Emulsion layer with a different, non-photosensitive development nuclei containing Brought into contact with the receiving layer and developed in a developer containing a solvent for the Contains halogen silver. In this case, during the image formation in the emulsion layer on the not complexes sufficient amounts of halogen silver to exposed parts of the photosensitive material, which diffuse over into the non-light-sensitive receiving layer and there through the reducing Effect of the developer, which catalyzes through the development nuclei present in the receiving layer will create an image.

This principle of diffusion transfer method is used in many offices for fast copying of Letters, documents and drawings applied. In general, you can only do one make a usable copy, although the amount of silver used is only a small part of the available Represents the amount of halogen silver in the unexposed parts of the halogen silver emulsion layer, so that theoretically it is possible to produce different prints of the same picture. It is but it is often necessary to make several copies of an original as quickly and cheaply as possible. However, if you can attempts to make even one additional copy of the same recording by bringing the negative into contact with a second image receiving layer and following that described above If the process leads through a special developer solution, the result is completely inadequate.

Attempts have already been made to produce several prints from a recording by placing it in the developer solution decreasing concentrations of halogen silver solvent used (A. J. Sievers, Phot. Soc. of America, Technical Quarterly, May 1955, pp. 75 to 78).

It is also known to add fixing accelerators to the developing bath in addition to the halogen silver solvents. Adding desensitizers for the latent image and plasticizers for the gelatin (USA.Patent 2,834,676).

Silver complex diffusion transfer process

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 September 24, 1959 (no.243 731)

Albert Emiel van Hoof, Benhem, Antwerp,

Dr.-Chem. Rene Maurice Hart
and Dr.-Chem. Jozef Frans Willems,

Wilrijk, Antwerp (Belgium),
have been named as inventors

All of these means, however, give fairly weak and less intense images, with the number being good Copies is limited to a maximum of four or five. It is also known to take a number of prints and produce the same recording by complexing the unexposed during the process Halogen silver is inhibited, which is achieved by adding compounds that slowly release halogen ions, to the image receiving material or to the bath or by the presence of excess alkali halide takes place during the course of complexation (Belgian patent 545 312).

It has now been found that one and the same image can be used to produce a number of well-covered copies by the silver complex diffusion transfer process if water-soluble basic polymers are added to one or more layers of the image-receiving material which have hetero-nuclei in the side chain which in turn contain a quaternary nitrogen atom.
Examples of such polymers are:
Poly (l-methyl-2-vinylpyridinium iodide),
Poly (l-methyl-2-vinylpyridinium methyl sulfate),
Poly (l-methyl-4-vinylpyridinium iodide),
Poly (l-methyl-4-vinylpyridinium methyl sulfate),
Poly- (I-vinyl-3-methylimidazolium iodide) and
Poly (1-vinyl-3-methyimidazo lumbar methyl sulfate).

109 740/483

3 4

The "compounds used according to the invention" sticks firmly to the negative material in the following however, if the adhesive strength gradually decreases in different layers of the image-receiving copies, see above Incorporate materials, provided they are with the components that-last copies because of the lack of Konaus which this layer (s) are built up, contractually tact between the photosensitive film and the are. It is thus possible for the image-receiving sheet according to the invention to appear blotchy. The adhesive strength bonds of a pre-layer, post-layer, barite layer between light-sensitive layer and image receiving or even add to the paper itself, although the material must not be so high that the separation The preferred method is that it becomes difficult to germinate the two materials. The right one to incorporate a layer. It was further stated that value can be achieved by clicking on the the cheap image receiving material achieved with the basic polymers ixnd / or the photosensitive effect on the type of germs used, depending on the material borrowed, but preferably on the image empist. capture material and the photosensitive material, a

Development nuclei, which act as reducing nuclei for the layer of a hydrophilic, water-soluble, highly

Complexed halogen silver come into question, are molecular substances or mixtures of such substances

among other things, colloidal silver, sulfur and collo- * 5 applies. These substances or colloidal binders

ideal metal sulfide, such as copper, nickel, tin, natural, semi-synthetic and fully synthetic

Silver and zinc sulfide. Other connections serve to be table materials. Suitable binders are

not as germs themselves, but can be caused by gum arabic, tragacanth, pectin, cellulose derivatives,

act with the diffusing silver complexes such as methyl cellulose, hydroxyl cellulose and carboxy-

form such germs, either through re a ° methyl cellulose, polyvinyl alcohol, partially hydrolyzed

production, as in the case of stannous chloride, or by based polyvinyl esters, such as polyvinyl acetate, polyvinyl

Formation of poorly soluble compounds with sulphyrrolidone, dimethylhydantoinformaldehyde resin, etc.

fiden or organic compounds that are easily further found to be the germinal layer of the

Sulfur in the form of a divalent ion ab- image receiving material such as gelatin as

split like thiosinamine. 25 binder contains, with good success, also hydrophilic

In order to achieve the highest possible image coverage, high molecular weight substances can be added to it is recommended that the additive according to the invention is gluing the image receiving material on the lichtin Presence of not too small development-sensitive material at a favorable value too to germinate. This can be done by keeping. At the same time, they are capable of high molecular weight that the colloidally dispersed germs in an environment 30 substances to form the coverage of the image receiving material that contains only a small amount of protective colloid. mend what in all likelihood is at a

It has not yet been clarified why increased reactivity of the germs obtained in this way when used

of these polymers more intensely covered copies can be traced back to the coating.

stand; It is assumed that the soluble halogen In this case the production of the image silver complex from the light-sensitive emulsion-receiving material can be carried out in a very simple manner, diffuses over into the image-receiving material because only a single layer is on the support, exemplified and in it by the Presence of the basic white paper, must be applied.
Polymer is precipitated in compact form. At the same time, it was noted that hardening the colloid at the same time would in this way shift the diffusion uniformity of both the image receiving material and the weight in favor of the image receiving material of the highly sensitive material of the formation of a. uniform and sufficiently high density of the image

A further intensification of the image coverage can counteract the receiving material. Indeed it will can be achieved in that one of the layers by adding hardeners to colloid layers of the image receiving material small amounts of haze, which reduces the permeability, which prevents diffusion Agents such as phenyl mercaptotetrazole, benzine 45 transfer of the complexed silver salts from the triazole, mercaptobenzothiazole, etc., added. light-sensitive layer into the receiving layer

The invention offers the advantage that the usual. Because of this, they have been very successful

Chen development baths and devices for the silver swelling agent at least one of the layers of the light

complex diffusion transfer process without changing sensitive material or image receiving

tion can use. With a device that added the usual 5 ° materials, making copies with higher density

Borrowed developer solution contains, so you can both have been obtained.

Individual copies according to the known method as well as Various swelling agents are known, ζ. Β

multiple copies of a recording after the process urea, water-soluble thiocyanates, nitrates and

of the invention. Halides, such as potassium thiocyanate, potassium nitrate,

Halogen silver emulsions, which are suitable for the invention 55 sodium nitrate, potassium iodide, barium chloride, calcium

suitable procedures include chlorobromosilver chloride and magnesium chloride, ammonium salts,

emulsions, silver bromide emulsions containing chlorosilver sodium salicylate, formamide, dimethylformamide,

and chlorosilver emulsions; all these emulsions ethylene chlorohydrin, chloral hydrate and "-naphthalene-

If necessary, small amounts of iodized silver disodium sulfonate can be used.

keep. For rapid diffusion transfer of the 60 The best results, however, were with urea

However, complexed halogen silver are preferentially achieved. This product can be used in the light-sensitive

wise emulsions used, which mainly chlorine borrowed and / or the image receiving layers in quantities

silver included. However, if you strive for the shortest possible addition, the 5 to 80% of the weight of the in these

Exposure times, so it is advantageous to have sensitive layers of binder present.

Use bromide silver emulsions that are as low as 65 µm compared to the copies produced according to the invention

Contains quantities of silver chlorine. better looks and longer life too

It has also been found that when making these copies, one can add to that for making these copies

of several copies, although the first copy provides sufficient image-receiving material connections

Claims (1)

5 6 remain, which prevent the discoloration of the material, suspension is poured according to Example 1, with the such as, for example, organic halogen-containing phosphones, but the difference is that instead of poly (l-vinyl-3-methyl- acid and phosphoric acid esters, as in the Belgian imidazolium methyl sulfate) 0.4 g poly (l-methyl-4-vinyl- Patent 580,250 is described. pyridinium methyl sulfate) is used. After another The following examples serve to illustrate the 5 treatment as in Example 1, ten sharp Invention, without limiting it in any way, copies can be made of a recording. ken. ". . , " . , Example 3 example 1 A photosensitive material is, as in the case of A photosensitive material is produced, io game 1 produced. by applying an image-receiving material as in Example 1 to a cardboard-thick paper of 200 g / m ² high-contrast silver chlorine emulsion is poured, too, but with the difference that in the the per kilogram of emulsion 35 g urea and 50 g seed layer composition the poly (I-vinyl-3-me- Corn starch can be added. thylimidazolium methyl sulfate) by 2.5 g of poly (l-me- On this emulsion layer is then a 1% ^El 5-thyl-2-vinylpyridinium iodide) is replaced, Poured aqueous carboxymethyl cellulose solution. After further treatment as in Example 1 can An image receiving layer is made by making ten sharp copies of one picture on paper of 90 g / m ^{2 become} a seed layer of one. Suspension of the following composition cast Example 4 becomes: ao C gelatin 40 e ^Em li ^cntem pfi ⁿ dliches material is as in examples Colloidal 'Zinc Suifid ''.'.'.'.'.'.'.'.'.'. 0.24 g ⁸ P ^ ^l Sf ⁵ ^ ₊ ........ ... ... Sodium thiosulphate (anhydrous) ... 4g. ^The receiving material is as in Example 1 Phenylmercaptotetrazole ......... 0.1 g produced but with the difference that in the Poly (l-vinyl-3-methylimidazolium ²⁵ seed layer composition, the poly (l-vmyl-3-me- methvlsulfaf) 0 6s thylimidazolium methyl sulfate) by 0.4 g of poly- (l-me- Water up to 1000 cm ^{3 of} thyl-4-vinylpyridinium iodide) is replaced. After further treatment as in Example 1 can In this second layer is / _o solution of ten sharp copies of a recording made one of a 2 ° aqueous carboxymethyl cellulose solution existing 3 °.
Layer applied. A photosensitive film is imaged in accordance with the patent claims: exposed and in a known manner with an image-receiving 1. Photographic silver complex diffusion film in the presence of a developer of the following transfer method, in which to manufacture Contacted composition: 35 multiple copies of an exposed halosilver anhydrous Sodium sulfite 65 g emulsionsclucht developed and undeveloped Hydroquinone 14 g of remaining halogen silver for image-correct diff- l-Phenyl-3-pyrazoiidön ". '.'. '.'. '.'. '.'. Ig are each founded in an image-receiving layer Sodium hydroxide 11g * ™ ** ^{is' m} * ^{n the} presence of development Potassium bromide. Ig ⁴⁰ lung germs a copy is produced thereby Water up to 1000 cm ³ characterized that an image receiving material is used, the water- After 5 seconds, the two sheets of insoluble basic polymers were added, other separated; then the photosensitive film will carry the hetero nuclei in the side chain, which contain a quaternary nitrogen atom in the same way with a second image-receiving sheet 45, brought into contact and again after 5 seconds 2. The method according to claim 1, thereby marked. By repeating this procedure, one can draw the halogen silver emulsion ten clear copies of one and the same layer and / or the image-receiving layer urine absorption getting produced. fabric adds. ... 50 3. Photographic image receiving material for example 2, _the process according to claims 1 and 2, characterized in that a light-sensitive material is produced as in the case where it contains water-soluble game 1. basic polymers, which are in the side chain. An image receiving material is produced by ^{having hetero cores which contain a quaternary stick on paper of 90 g / cm 2,} a seed layer of one atom of substance. 1 109 740/483 11.61