DE1472896A1 - Photographic quick copy process - Google Patents

Description

The invention relates to the rapid processing of photographic copies, in particular rapid fixing and stabilization of copies.

JSs are known procedures that are used in rapid treatment silver images are produced from photographic materials, without the need for the conventional fixing and washing baths are. This is developed in the usual way, then with a solution of a stabilizer such as ammonium thiocyanate, treated and dried immediately afterwards without washing. The otherwise usual fixation treatment is not required and it saves time. Various such rapid treatment methods are e.g. B. described in H.D. Russell, B.O. Yackel & G.S. Bruce, Photo-Graphic Science and Technical Journal 195o August pp. 59-62 as well as in the United States patent documents 2,614,927 and 2,448,857.

In this rapid treatment process, uby siermittel uses a compound that has S or SH groups

BATH ORIGINAL

contains, ζ. B. alkali or ammonium biocyanate, alkali or ammonium thioulfate, thiourea or thioglycol. These stabilizing agents allow rapid treatment, however, the copies show defects in quality.

In order to ensure the lightfastness of the copies, you have to the otabilizing agent in a considerable excess apply over the theoretically calculated amount. In this way, the hygroscopicity of the stabilizing agent prevents a the copy dries completely and the surface becomes sticky. Since the stabilizer gradually becomes metallic If silver oxidizes to a complex salt, the image density decreases or disappears and the hue changes from black to brown or yellow. These depressions appear especially if copies are stored in higher humidity. When the copy is exposed to your light, in a point in time when the reaction between the undeveloped halosilver and the otabilizing agent has not yet ended photodecomposition of the non-congested Halogen silver and stains appear in the white and transparent areas.

The invention was based on the task of eliminating these deficiencies in terms of rapid treatment and improving the quality of the copier . In addition to the salt density in the behände it? / Ι photosensitive layer decreases and achieving üc ■ β so-called "Ferro type finishes" are made possible. Lef ti ·; ;; a is a treatment to smooth the surface by means of Au-

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pressing a warm metal plate and could either not be used at all or the copies gradually lost their luster with the copies made by means of the known Sohne 111) treatments and prevents the yellow or orange discoloration that occurs when exposed to light with ultraviolet rays, e.g. B. sunlight arises.

According to the invention, the photographic layer stabilized by means of ammonium thiocyanate and / or alkali thiocyanate is applied for a short period of time, which is preferably between 1 and 10 minutes: i ) s, \ r. _r treated with a solution which contains the same or greater Thiccyanetverbindungen in a concentration of 1 to 15 Gev; .. ». The concentration of this solution should be lower ^ eIz ^ λ.? Jie Kor ^^ ntration of i "^ iocyanate in the stabilizing solution.

If the concentration is lower than 1 70, thiocyanates flow out from dex photographic layer and the stabilizing is insufficient. If the concentration is over 15 #, the Kenge of thiocyanate in the photographic layer is increased to an N- unnecessary excess and the metallic syllable. "? In the image is easily attacked.

The aim of the tendon is to develop and develop Stabilization at the latest within a limit, usually in less than 10 seconds to finish. Desnalb v.ird the concentration of the otatilisieruittels as high as possible

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taken

Where. Almost all stabilizers have an extreme high solubility. The high concentration required for a high rate of stabilization was obtained a high salt density in the photographic layer, which enhances the hygroscopic properties, the layer sticky or blotchy and fading.

As a countermeasure, it is known to use precious metal salts and Add organometallic excapto compounds, thiosulphates together to be used with Kiiooyanaten (E. T. Smith and G. W. W. Stevens j USA Patent 3 132 943) and to add alkali or ammonium sulfites, bisulfites or metabisulfites. By These hatreds can be caused by the disappearance of the silver image and the discoloration of the white and the transparent area can be reduced, but the effect is not complete and the stickiness of the surface is hardly reduced.

In contrast, in the method of the invention, the tackiness of the surface is almost completely eliminated and obtained the same surface properties as can be achieved with normal fixing and washing treatments. the Copies can therefore get the ferrotype finish with warm metal plates and keep them even after this treatment, their shine for a long time. By adding a fluorescent whitening agent (optical brightener) or a Noble metal salt, an organomer capto compound or of Thioeulfat in the second used according to the invention Stabilizing bath, the shrinkage of the silver image and the degree of whiteness can be further improved.

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According to the invention, the stabilization is essentially carried out in two stabilizing baths. However, if you increase the time for the initial stabilization, you can also stabilize the copy and have similar effects.

Examples follow to further illustrate the invention. example 1

To produce the photosensitive paper, a Chlorosilver gelatin emulsion containing hydroquinone Applied to baryta paper, flat of exposure and development was treated with a stabilizing solution of the following composition:

Water (50 ° C) ammonium thiooyanate Na tr iumb i sulf i t

Sulfuric acid e-monomethyl-p-aminophenol

1-phenyl-5-thiotrtetrasol (1 # Lge alcohol solution) CoSO ₄

Water to make up to 1 liter

If the treatment is carried out at tree temperature, development and stabilization takes about 10 seconds completed. A stabilized copy is obtained in half-trooken State. The surface does not show such a gloss as a copy with a ferrotype finish.

The second stabilizing bath contained the

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5oo ecm 25o S. 7o G 2 G 6o com o, 5 β

siθxbad described solution, but in six-fold volume dilution. After three minutes of immersion and slight deviating the excess solution was placed in a ferrotype machine. She was then equivalent to one Copy that of the normal fixation, washing and ferrotype finishing treatment was subjected.

For comparison, copies made only through a stabilizing bath and the gloss was measured on copies that had passed through the two stabilizing baths. the Measurements were made with a gloss meter at an angle of incidence of 6o °. The results are shown in the following table:

Treatment Directly after Ferrotype - 2 weeks after Ferro-

Finish type finish

1. Stabilizing

bath 65 59

1st and 2nd stabilizing bath 10098

The table shows that the gloss increases both immediately after the ferrotype finish treatment and two weeks later the copies that according to the invention by two Stabilisierbädejf gone is significantly better. The decrease in gloss after storage is also much less than with only once stabilized copies.

The copies were initially made in the same solution as in Bei game 1 (first stabilizing bath) stabilized. Then was for 5 minutes in an aqueous solution of 3.5 wt.% Ammonium thio

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oyanate (second stabilizing bath) and then immersed the ferrotype finish was carried out. The same results as in Example 1 were obtained.

Example 3

In the working method described above, the Second stabilizing bath uses an aqueous solution of 4% by weight of potassium thiooyanate. The copies had the same properties as in Example 1.

Example 4

■ Sin barite paper with a bromide berry gelatine coating of low bromide content was exposed and developed using the surface treatment process with a solution of the following composition:

Sodium hydroxide 22.5 g Sodium sulfite, anhydrous 8o g Hydroohinone 36 g

Pyraeon 2 g

Potassium bromide 0.5g Waaaer earn topping up to 1 liter

The developed paper was placed in a first stabilizing bath

the following composition:

lallumthlooyanate 3oo g

LaUummetabisulfit 5o g

Vatzium sulfite, waeaer-free 15 β

liaesaig 4o ecm

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Sodium phosphate (Na ₂ HPO ^) 15 g

Water to fill up to 1 idter

After the first stabilization treatment had been carried out as in Example 1, the mixture was placed in the second stabilizing bath for 3 minutes immersed. This contained 4% by weight of ammonium thiooyanate and 0.1% by weight of a fluorescent whitening agent, z. B. Whitex 3B (Sumitomo Chemical Industry Co.) Then became the ferrotype finish treatment is carried out.

The copy had the same properties as in example 1, an extremely high degree of whiteness and a sharp image contrast.

In the drawings are the spectral reflectance curves for the double stabilized copy according to the invention (curve II) and for a copy treated only in the first stabilizing bath (Curve I). Big. 1 shows the spectral reflectance immediately after the ferrotype finish treatment. Aussex in Area of 4oo ΐημ there is not much difference between curves II and I Fig. 2 shows the spectral reflectance, after the copies have been exposed to daylight for 24 hours The worsening of the whiteness (yellow coloration) is according to curve II in the case of the treated according to the invention Copy not significant, while curve II shows severe deterioration. Because the effect of the fluorescent Is not shown by means of the curves, the actual white and the copy II is not better than it can be seen from curve II.

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Example 5

With otherwise the same treatment as in Example 4-, for the second stabilizing bath uses a solution of 5% by weight of potassium thiooyanate and 0.5% by weight of Whitex 3B. At a The same results as in Example 4 were obtained for a duration of 1 minute. In addition, this solution has the advantage that it is more extensive, i. h. that one opposite of the solution of Example 4- a large number of copies can treat in her

Example 6

In otherwise the same treatment as in Example 4, a solution of 4 wt.% Ammoniumthiooyanat and 6 wt.% Potassium metabisulfite was used for the second stabilizer. With an immersion time of 5 minutes, almost the same results were obtained as in Example 4, apart from the effect of the optical brightener.

Example 7

When using less glossy paper, e.g. B. with matte or semi-matte paper or with papers with special surface properties, such as Seidenga ^ Lnz or Fine grain surface, the first and second stabilization, as indicated in the previous examples, with the difference that the ferro-type finish treatment is carried out on the reverse side of the paper. In these cases, too, the tendency to Yellowing from daylight and surface tackiness improved.

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Claims (1)

Procedure for sonel treatment in the case of hera division photographic copies, characterized in that the photographic material after development in a first stabilizing bath, the ammonium and / or Alkalithiooyanat contains, is treated and then immersed in a second stabilizing bath, the Contains at least one of the stabilizers mentioned in an amount of 1 to 15% by weight and which is then dried. 809810/1263