DE1961029A1 - Process for making photographic images - Google Patents

Description

AGFA-GEVAERTAG

PATENT DEPARTMENT

LEVERKUSEN

^{Za / AS} ■ *. Dec 1969

Process for making photographic images

The invention relates to a method for producing photographic Images by imagewise generation of catalase-active and / or peroxidase-active catalysts by exposure a photosensitive layer and image-wise decomposition of peroxide compounds on these catalysts, whereby by image-wise generation of gas bubbles by physical means or by color-giving image-wise reaction of the resulting Oxygen with a suitable action component a visible image is created chemically.

In addition to the conventional photographic processes, the Using light-sensitive silver halide emulsion layers, numerous other methods of preparation are already in place photographic images known. For example, you can create bubble images by using a photographic material produce a layer with a dispersed in a binder light-decomposing compound, e.g. contains diazo salts. If such a material is exposed imagewise, so the compound decomposes according to the exposed Picture, where a gas is set free. The subsequent heating of the exposed material causes them to expand the gas bubbles out, and a bubble image is created. Since the obtained vesicles scatter the light image-wise, appear These areas are dark in transmitted light, but light when viewed in reflected light. In the unexposed areas

A-G 561

109824/1625 BADQRlGfNAL

form 4341. 7m / 5

Aue of the Belgian patent 725 903 is also the Production of photographic images known, consisting of a silver image and a vesicle superimposed on the silver image exist. According to the method described there, a silver image is first created on a conventional layer in a hydrophilic layer Generates paths, which, however, has a much lower coverage than the conventional black and white images that are usually produced. The layer is then brought into contact with hydrogen peroxide, whereby, at the points that the Siib.er contained imagewise in finely divided form, the hydrogen peroxide is decomposed with the formation of oxygen gas bubbles. This achieves an extraordinarily high level of enhancement of the silver image and, when used, even results in a very low silver content Layers of deep black images with extremely high contrast. Even if the quality of this procedure photographic images obtained is quite satisfactory, this method is disadvantageous in that it is initially carried out customary conventional development a silver image must be generated, which in a second processing stage with hydrogen peroxide is implemented to generate the congruent bubble image. This makes the processing relative laborious.

The other known photographic processes without Silver halide layers are generally of little practical use because of their low sensitivity to light Interest. In contrast to conventional silver halide photography namely, the light yield in such photosensitive systems is relatively low, since only one that provides color photochemical metabolism of one molecule per absorbed light quantum is possible. A reinforcement effect like at the development of the conventional exposed silver halide emulsion layer en, does not exist here.

AG 561 - 2 -

109824/1625

The invention is based on the problem of silver halide-free to develop photographic recording processes that are as easy as possible to convert to black and white or colored images with sufficient contrast.

There has now been a method of making photographic Images by exposing a layer containing jtoffe, those which are catalase-active or peroxidase-active when exposed to light Form catalysts and then treat with a peroxide compound to form a visible image found using a photosensitive layer which contains compounds which split off iodine ions when exposed to light.

Iodoform or derivatives thereof are suitable, i.e. compounds that contain a Trij ο dme thy! Group, e.g. those of the following Formula:

H-CJ ₃

wherein R (I) is hydrogen, (II) a saturated or olefinic one unsaturated aliphatic ^ group with preferably up to 5 carbon atoms such as methyl or ethyl, these radicals in turn can be substituted, for example, with halogen or phenyl, (III) aryl, in particular a ring of the phenyl series, (IV) carboxyl or esterified carboxyl (V) carbamoyl, (VI) nitrile, (VII) aldehyde or (VIII) is a heterocyclic radical.

With normal exposure, they are him! xten pictures handy not visible. They are made visible with peroxide compounds, for example hydrogen peroxide in contact brought. The peroxide compound is imagewise formed at the points where the decomposition catalysts are formed have activated.

The visualization of the image by means of the activated peroxide can now take place physically or chemically. So can the evolved oxygen e.g. after the in the

AG 561 - 3 -

109824/1625

Make the above-mentioned Belgian patent 725 903 process visible as a bubble image. It is further possible to the peroxide compounds in the presence of reaction components for a coloring oxidation fraction decompose. Such methods are in the German patent specification (P 18 13 920.3).

The layers according to the invention preferably contain the light-sensitive iriiodomethyl compounds in a binder dispersed. Suitable binders are e.g. pebbles, polyvinyl acetate, partially saponified polyvinyl acetate, polyvinyl alcohol, Cellulose esters such as cellulose acetate or cellulose butyrate, carboxymethyl cellulose or natural binders, fc in particular proteins such as gelatin.

However, the triiodomethyl compounds can also be attached directly to the substrate can be added by treating the carrier with a solution or dispersion of the triiodomethyl compound.

The concentration of the triiodomethyl compounds in the photosensitive Material can fluctuate within wide limits. Concentrations between 0.3 and 5 g have proven to be suitable per square meter of photosensitive material. The optimal amount for the respective reproduction process can be determined by a few simple manual tests can be determined.

ψ as peroxide compounds are inorganic peroxide compounds for the inventive method, for example, perborates ,, JPejrcarbonate or persulfates, however, particularly useful hydrogen peroxide. Organic peroxide compounds, such as benzolyperoxide, can also be used. Because of its effectiveness and easy handling in the form of aqueous solutions, hydrogen peroxide is preferably used. j

The peroxide compound is preferably used in dissolved form. Hydrogen peroxide, for example, can also be found in Be applied in vapor form.

ArG 561 - 4 -

109824/1625

ORIGINAL iNSPECTED

For the production of a bubble image, the exposed Layer heated during or after treatment with hydrogen peroxide. This forms in the places where pictorially the decomposition catalysts have formed, a picture of bubbles the end.

The strength of the vesicle depends on the amount of the hydrogen peroxide used, as well as the amount of decomposition nuclei formed. The heat treatment the material used to generate the visible bubbles should be as short as possible. The here to be observed The temperature depends on the properties of the binder. Satisfactory results can already be achieved with relatively reach low temperatures of around 60 - 70 °. However, higher temperatures can also be used, if the softening point of the binder requires it. When using the preferably suitable gelatin as a binder it is advisable to work in the presence of small amounts of water, as this causes the gelatine to swell and thus, the formation of bubbles is promoted. The same applies to other binding agents that swell with water.

According to a preferred embodiment, the exposed Layer after the treatment with the hydrogen peroxide vapor for a few seconds, e.g. 1.5 seconds in a waaser vapor atmosphere exposed from about 50 - 90 °. This occurs only slowly during treatment with hydrogen peroxide alone Blistering occurs very quickly. The layer treated with hydrogen peroxide has proven to be even more beneficial to expose to an alkaline water vapor atmosphere, pH values between 8 and 12 are suitable. This can be done easily can be achieved by adding small amounts of ammonia or vapors of volatile amines to the water vapor. The concentration of the alkaline additives is not critical. In general, amounts between 0.1 5 Volume - #, preferably about 0.3-1 volume- ^ as sufficient proven.

AG 561 - 5 _

109824/1625

The visible image can also be produced chemically that the treatment of the exposed layer with the peroxide compound in the presence of reaction components is carried out for a coloring oxidation reaction. Suitable Methods are in the German patent specification ....

(P 18 13 920.3). .

The formation of color by peroxide is also faster if the layer is exposed to a brief steam treatment has been subjected.

Of course, they are preferably suitable for oxidative dye formation those reaction components that produce the deepest possible colored compounds in the oxidation with the catalytically activated Give peroxide compound.

Saber, the reaction components can be organic Act compounds which provide the image dye even when oxidized, 2.B. Amino, hydroxy or amino hydroxy compounds of isocyclic or heterocyclic aromatics. '

Examples include: phenol, aniline, pyrocatechol, Resorcinol, hydroquinone, o-, m- and p-phenylenediamine, N, N-dimethylphenylenediamine, Ν, Ν-diethyl-phenylenediamine, N, N-ethylmethyl-phenylenediaoin, o-, m- and p-aminophenol, p-methylaminophenol, 2,4-diaminophenol- (1), 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6,7-trihydroxynaphthalene, 1,2-diaminonaphthalene, 1,8-diaminonaphthalene, benzidine, 2.2 - Diaminonaphthalene, 4,4'-diaminodiphenyl, 8-hydroxyquinoline, 5-hydroxyquinoline, 2-hydroxycarbazole, 1-phenylpyrazolou- (3) and other.

The amino, hydroxy or amino hydroxy compounds can also be substituted, e.g. with halogen, alkyl, aryl, alkoxy, sulfonic acid, nitro, keto, carboxylic acid or carbonamide groups. Examples include: 2,5-dichloro-p-phenylenediamine, guaiacol, 4-methoxynaphthol (1), 1-hydroxy-2-aminobenzene-4-sulfonic acid,

A-G 561. - 6 - ■

109824/1625

i-Amino ^ -hydroxybenzene ^ -sulfonic acid, 3-Araino-5-sulfo-salicycls aure e, 1,6,7-irioxynaphthalene-3-sulfonic acid, benzidine-2,2 »- disulfonic acid, benzidine-3,3'-olisulfonic acid, 1,8-dihydroxynaphthalene-disulfonic acid- (3,6), 4-nitro-benzatechol.

In some cases also show mixtures of several such Compounds in the process of oxidation produce a much stronger dye than the individual components. For example, a A fortified mixture of o-phenylenediaain and catechol Dye formation. Even components which by themselves do not give off any dyes when oxidized, such as e.g. letrabromohydroquinone or tetrabromopyrocatechol, when added to other hydroxy, amino or amino hydroxy compounds increase dye formation.

The oxidation of the aromatic amino, hydroxy and / or amino hydroxy compounds gives rise to monomeric or polymeric dyes related to the quinone imines and azines. Some examples of this oxidative dye formation are described by H.R. Swiss, "Artificial organic dyes and their intermediates", Springer-Verlag Berlin-Göttingen-Heidelberg (1964), pages 222, 275, 281 and 293; N. I. Worozhov, "Basics of Synthesis of intermediate products and dyes ", Akademie-Verlag Berlin (1966), pages 703 to 789; A. Schaeffer," Chemie der Dyes and their application "(Technical Progress Reports, Volume 60), Theodor Steinkopff-Verlag Dresden-Leipzig (1963), Pages 59 ff.

In addition to dye precursors, there are of course also leuco dye compounds and vat dyes which can be oxidized to dyes can be used. For examples, see MR. Swiss, "Artificial organic dyes and intermediates", Springer-Verlag Berlin-Göttigen-Heidelberg (1964), pages 250 and 320.

For the process according to the invention, those oxidizable organic compounds are also suitable, which only in one Follow-up reaction with other compounds give rise to the image dye. In principle, all reaction systems are useful

AG 561 ~ ⁷ "

109824/1625

which lead to dyes under oxadative coupling. Reference is made in particular to the so-called color photographic developers of the phenylenedismine or aminopyrazolone series (cf. z * BCE K · Mees and TH James, "The Theory of the Photographic Process", 3rd edition, MacMillan Co. New York (1966), Page 382; JR Schweizer, "Artificial organic dyes and their intermediates", Springer-Verlag Berlin-Göttingen-Heidelberg (1964), page 295). Isocyclic and heterocyclic hydrazines can also be oxidatively coupled to dyes with suitable components (cf., for example, H. Hünig at al., Angew. Chem 70 (1958) 215? S. Hünig, Chimia 15 (1961) 133 and Angew. Chem. 74 (1962) 818). The color-imparting photographic developer substances are catalytically oxidized by the peroxide compounds on the image-wise distributed catalyst. Their oxidation products can then react with known photographic color couplers, which are also present, to form dyes. All color couplers are suitable for this, for example those of the phenol or naphthol series as blue-green couplers, the indazole series as magenta couplers and the benzoyl canilide series as yellow couplers.

example 1

Manufacture of the photosensitive material:

A layer of the following casting solution is applied to a layer support made of cellulose acetate

50 ml of a 2 # solution of i% iodoform, ethanol 100 ml of a 6 # aqueous gelatin solution 5 ml of a 30 # aqueous solution of formaldehyde

Processing!

The dried layer is exposed in a conventional sensitometer behind a gray step wedge (exposure time 10 seconds with a 100 watt lamp). Subsequent will be the

A-G 561

109824/1625 originally inspected

Layer in a water vapor atmosphere for about 1 minute about 70 ° extended. Now watering is carried out for 10 minutes, then the layer can be exposed to daylight. You get with this treatment, a barely visible blue image of the original.

The image is enhanced by bathing the layer in a bath of the following composition for 15 minutes!

20 g Ν, Ν-diethyl-p-phenylenediamine sulfate 1 g pyrocatechol
to 1 1 H ₂ O
adjusted to pH = 6 with Na _{2 CO.}

Shortly before use, this solution is still 50 ecm one 30 # aqueous solution of hydrogen peroxide was added.

A deep black negative image of the original is obtained. By the enhancement bath, the optical density of the image has been enhanced by about a factor of 100. In conclusion, will Watered for 15 minutes.

For bubble formation, the layer is about 30 seconds with saturated hydrogen peroxide vapor from 70 ^ö bahandelt and exposed d 1/2 second a steam atmosphere of 75 °.

It occurs immediately, extraordinarily, through the formation of vesicles great amplification effect, e.g. a point with a density of 0.05 of the original image in directional white Licirfc is increased to 1.8.

561 - '- 9 -

109824/1625

Claims (5)

Claims AO (Ω Process for the production of photographic images by exposure of a layer which contains substances which "form catalase-active or peroxidase-active catalysts on exposure and subsequent treatment with a peroxide compound, characterized in that a photosensitive layer is used which contains a compound, which "splits off iodine ions when exposed to light. 2. The method according to claim 1, characterized in that a photosensitive layer is used, the iodoform or contains derivatives thereof. " 3. The method according to Asnprüchen 1 and 2, characterized in that the exposed image with a peroxide compound is treated, which decomposes on the imagewise formed catalysis-active catalysts with the formation of oxygen is and then expanded by heating the layer, the resulting gas to form a bubble image will. 4. The method according to claim 1-3, characterized in that Mixtures of peroxides and hydrazines can be used to create the vesicle pattern. 5. The method according to claims t-4, characterized in that that the exposed layer with peroxide compounds in the presence of reaction components for a coloring Oxidation fraction is treated. A-G 561. -10 - 109824/1625