DE1955901A1 - Process for making photographic images - Google Patents

Description

AGFA-GEVAERTAG

PATENT DEPARTMENT

LEVERKUSEN

za-mka October 30, 1969

Process for making photographic images

The invention relates to a method for producing photographic ones Images by image-wise deactivation of catalase-active and / or peroxidase-active permeates by exposure to light a photosensitive layer and image-wise decomposition of peroxide compounds on these perments, whereby by pictorial Generation of gas bubbles by physical means or by color-giving image-wise reaction of the resulting Oxygen chemically creates a visible image with a suitable reaction component.

In addition to conventional photographic processes using light-sensitive silver halide emulsion layers, numerous other methods of producing photographic images are known. So you can, for example, bubble images by using a photographic material having a layer with one in a binder dispersed light-decomposing compound, e.g. contains diazo salts. If such a material is exposed imagewise, so

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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 the transmitted light when viewed In the reflected light, on the other hand, it is bright. In the unexposed parts of the layer, the incident light is essentially let through.

From the Belgian patent 725 905 the production is also known photographic images, which consist of a silver image and a vesicle superimposed on the silver image. According to the method described there, a silver image is first created on a conventional layer in a hydrophilic layer Paths created, which, however, have a significantly lower coverage than the conventionally produced conventional ones Black and white pictures. The layer is then brought into contact with hydrogen peroxide, where the Contain silver in finely divided form, the hydrogen peroxide with the formation of oxygen gas bubbles is decomposed. This achieves an extraordinarily high level of reinforcement of the silver image and, when used, is obtained by itself very low-silver layers produce deep black images with high contrast. Even if the quality of this procedure photographic images obtained is satisfactory, so is this process is disadvantageous in that it first produces a silver image by customary conventional development must be, which in a second processing stage with hydrogen peroxide to generate the congruent vesicle image is implemented. This makes processing relatively cumbersome. You can also use this procedure only negative images of the original are received directly.

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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 color-providing photochemical metabolism of one molecule per absorbed light quantum is possible. A reinforcement effect as in the development of the conventional exposed one Silver halide emulsion layers are not present here.

The invention is based on the problem of being as free from silver halide as possible photographic direct positive recording processes to develop that with the simplest possible processing to black and white or color images with sufficient Lead contrast.

There has now been made a method of making positive photographic prints Images by imagewise exposure of a layer and subsequent treatment with a teroxide compound with the formation of a visible image using a photosensitive layer which is in uniform Distribution contains catalase-active or peroxidase-active ferments, which are formed imagewise by exposure to actinic light deactivated.

Practically all ferments are purely for the process according to the invention suitable, which are photosensitive, i.e. which are deactivated under the action of light and which are capable are to catalytically decompose peroxide compounds. Exemplary catalase, peroxidase, hemoglobin or hemin may be mentioned. '

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The photosensitivity of the layers can be increased significantly by adding compounds that act on exposure image-wise splitting off products which act as poisons for the ferments to be used in the manner according to the invention, i. which additionally deactivate these ferments at the exposed areas. Since the to be used in the manner according to the invention Catalase-active or peroxidase-active ferments generally contain complex-bound iron, are for this purpose preferably those inorganic or organic substances which split off halogen or cyanide on exposure to light.

Suitable inorganic halides which split off P halogen on exposure are silver halides, e.g. silver chloride, Silver bromide or silver iodide. Usable organic Halides are aliphatic with a tribromine or triiodine grouping, e.g. iodoform, tribromoethanol or tribromoacetic acid, or highly halogenated aromatic compounds, e.g. benzenes, which are substituted at least three times on the core with bromine or iodine, e.g. pentabromophenol. Connections of this kind are e.g. in British Patent Specification 957 192.

Of inorganic or organic cyanide compounds that are used in Release cyanide from exposure, in particular iron (II) or iron (III) cyanides or complex cyanides, and also nitroprussides mentioned, e.g. in the book by M.H. Ford-Smith "The Chemistry of Complex Cyanides", London 1964 are. In terms of organic compounds, reference is made to cyanides of triphenylmethane and its derivatives, such as from A. H. Spore, Trans. Faraday Soc. 57 (1961), 9-3.

The sensitivity can also be increased by adding compounds which generally act as electron acceptors will. Chloramil or tetracyano-p-quinondimethane, for example, are suitable.

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The exposure is preferably blue or ultraviolet Light used.

The images obtained on exposure are practically invisible. They are made visible with peroxide compounds, for example hydrogen peroxide, brought into contact. The peroxide compound is imagewise in the places where the Perments remained active, decomposed. Making the image visible by decomposing the peroxide can now be done physically or chemically Belgian patent 725 903 mentioned above Make the process visible as a bubble image. It is also possible to decompose the peroxide compounds in the presence of reaction components for a coloring oxidation reaction. Such processes are described in German patent specification (P 18 13 920.3).

The layers according to the invention preferably contain the light-sensitive perments, e.g. catalase or peroxidase dispersed in a binder. Suitable binders are e.g. silica gel, polyvinyl acetate, partially saponified polyvinyl acetate, Polyvinyl alcohol, cellulose esters such as cellulose acetate or cellulose butyrate, carboxymethyl cellulose or natural binders, especially proteins such as gelatin.

The perments can, however, also pass directly through the layer support Treating the carrier with a solution or dispersion of the ferment added.

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

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The same applies to the amount of additives that increase the sensitivity of the layers. Their concentration can also be within further areas fluctuate. Here, depending on the type of light-sensitive compounds, amounts between 0.2 and 5 g per square meter proved to be sufficient. The optimal concentrations and the optimal pair of compounds of the ferment and the susceptibility-increasing substance can through the usual tests can be determined in a simple manner.

The peroxide compounds used in the process according to the invention are inorganic peroxide compounds, e.g. perborates, percarbonates or persulfates, but especially hydrogen peroxide suitable. Organic peroxide compounds can also be used, e.g. benzoyl peroxide · Because of its effectiveness and ease of handling in the form of aqueous solutions, is preferred Uses hydrogen peroxide.

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

For the production of a bubble image, the exposed layer is used during or after the treatment with hydrogen peroxide warmed up. In the process, a vesicle image is formed at the points where the ferments have remained active in terms of image.

The strength of the vesicles depends on the amount of hydrogen peroxide used and the amount of resulting decomposition nuclei. The heat treatment of the material to generate the visible bubbles should be as possible take place briefly. The temperature to be maintained depends on the properties of the binder. Satisfactory Results can be achieved even at relatively low temperatures of around 60 - 70 °. It can, however higher temperatures are also used, if the

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Softening point of the binder requires this. When using The gelatin, which is preferably suitable as a binder, is recommended to be added in the presence of small amounts of water work, as this promotes the swelling of the gelatin and thus the formation of bubbles. Same goes for others water-swellable binding agents.

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 of a water vapor atmosphere from about 50 - 90 °, exposed. The treatment with hydrogen peroxide alone occurs only slowly occurring blistering occurs very quickly. It has proven to be even cheaper to treat those treated with hydrogen peroxide To expose the layer to an alkaline water vapor atmosphere, pH values between 8 and 12 are suitable. This can easily be achieved by adding little water vapor Amounts of ammonia or vapors of volatile amines are added. The concentration of the alkaline additives is not critical. In general, amounts between 0.1 to 5% by volume, preferably about 0.3-1% by volume, have proven to be sufficient proven.

The use of peroxides in a mixture with hydrazines is also very favorable for the catalytic generation of the vesicle pattern; then not only Op, but a (Op / E _? ) mixture is created.

The vesicle images obtained can, if necessary, according to the in

the German patents (P 19 00 540.1)

(P 19 00 864.1) against Moisture stabilized.

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 processes are described in German patent specification (P 18 13 920.3).

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They are preferably suitable for oxidative dye formation of course, those reaction components that are as possible result in deep-colored compounds in the oxidation with the catalytically activated peroxide compound.

The reaction components can be organic compounds, which themselves form the image dye during oxidation supply, e.g. 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-diethylphenylenediamine, N, N-ethylmethylphenylenediamine, 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 ^f -diaminodiphenyl, 8-hydroxyquinoline, 5-hydroxyquinoline, 2-hydroxycarbazole, 1-phenylpyrazolone- (3) and others.

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 Carb onamide groups.

Examples include: 2,5-dichloro-p-phenylenediamine, guaiacol, 4-methoxynaphthol (i), 1-hydroxy-2-aminobenzene-4-sulfonic acid, 1-amino-2-hydroxybenzene-4-sulfonic acid, 3-Amino-5-sulfo-salicylic acid, 1,6,7-trioxynaphthalene-3-sulfonic acid, benzidine-2,2 ^f -disulfonic acid, benzidine-3,3'-disulfonic acid, 1,8-dihydroxy-naphthalene- disulfonic acid- (3,6), 4-nitro-benzocatechol.

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In some cases they show too. Mixtures of several of these Compounds in oxidation a viej. stronger dye formation than the individual components. For example, a mixture of o-phenylenediamine and pyrocatechol results in a reinforced Dye formation. Even components that stand alone in the event of oxidation do not give any dyes, e.g. tetrabromohydroquinone or tetrabromo-catechol, when added to other hydroxy, amino or amino hydroxy compounds, the dye formation strengthen.

The oxidation of the aromatic amino, hydroxy and / or amino hydroxy compounds results in monomeric or polymeric compounds Dyes related to the quinone imines and azines. Some examples of these oxidative paraffin formations are described by H.E. Swiss: "Artificial organic dyes and their intermediate products", Springer-Verlag Berlin-Göttingen-Heidelberg (1964), pp. 222, 275, 281 and 293; N.I. Worozhov: "Basics of the synthesis of intermediates and dyes ", Akademie-Verlag Berlin (1966), pages 703 to 789; A. Schaeffer:" Chemistry of dyes and their application " (Technical port steps reports, volume 60), Theodor-Steinkopf f-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-GÖttingen-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 that lead to dyes under oxidative coupling. Be referred

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in particular to the so-called color-giving photographic Phenylenediamine or aminopyrazolone series developers (cf. e.g. G.E.K. Mees and T.H. James: "The Theory of the Photographic Process ", 3rd ed., Mac Millan Co. New York (1966), page 382; H.R. Schweizer:" Artificial organic Dyes and their intermediates ", Springer-Verlag Berlin-Göttingen-Heidelberg (1964), page 295) · Isocyclic ^ and heterocyclic hydrazines can also be used with suitable Coupling components oxidatively to form dyes (see e.g. H. Hünig et al., Angew. Chem. 70 (1950) 215; S. Hünig, Chimia 15 (1961) 133 and Angew. Chem. 74 (1962) 818). The color-giving photographic developer substances are on image-wise distributed catalyst oxidized catalytically by the peroxide compounds. Your oxidation products can then react with known photographic color couplers which are also present to form dyes. For this are all color couplers suitable, e.g. those of the phenol or haphthol series as a cyan coupler, the indazole series as a magenta coupler and the benzoylacetanilide series as a yellow coupler.

example 1

To 1 1 of a 5 ^ aqueous carboxymethyl cellulose solution to be in the dark for 100 cc of an aqueous 10 follow solution Ferri tribromoacetate complex compound (given as Halogenabspalter; prepared by bloating of excess Fe (OH) in 10 $ strength by weight sodium Tribromacetatlösung CBr ₅ - COOITa and filtering off the Fe (OH) excess). Then another 100 ecm of a 0.1 $ aqueous peroxidase solution are added.

The mixture is then cast into a thin layer on a paper support. Then it is hardened and dried by bathing in 1 consecutive Ba (NO,) p solution for 1 minute

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It appears with blue light behind a gray step wedge (Exposure time with a 200 watt lamp 10 seconds) exposed. The following solution is now used:

20 g 1,7-dihydroxynaphthalene s

40 g of phenylhydrazinesulfonic ^{acid (2)) as a} substance former on 1 1 H ₂ O

with Na ₂ OO, adjusted to p "= 11

5 cm of 30% H ₂ Op was added shortly before use

A black and white positive dye image of the original is obtained within 5 minutes.

At the end it is watered and dried for a further 15 minutes.

Example 2

To 1 liter of an aqueous 2% carboxymethyl cellulose solution are given in the dark as a light-sensitive halogen releaser 20 ecm of a dispersion containing 100 g of silver bromide and contains 20 g of carboxymethyl cellulose per 1 liter. Then 100 ecm of an alkaline 1 ^ ige aqueous Hemoglobin solution mixed in as a peroxidase-active catalyst. The mixture is made into a cellulose acetate support shed thin layer. It is then cured and dried as indicated in Example 1.

It is exposed to white light behind a gray step wedge (exposure time with a 200 watt lamp 1 sec.) and then treated with the following solution:

25 g 1-amino-naphthol (8) -sulfonic acid (A) \

10 g of 2-ethoxyphenol) ^{as a} dye former

on _f 1 1 H ₂ O

with Na ₂ CO, adjusted to ρ = 8

100 ecm of 30% H ₂ O _{2 were added} shortly before use

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A black and white positive dye image of the original is obtained within 5 minutes at 20. Finally, water and dry for another 15 minutes.

Example 5

In 1 1 of an aqueous solution of gelatin 50 g 6 follow Tribromäthanol be solved as Halogenabspalter in the dark. To this solution is then added 25 cc of a 0.1 followed by catalase. The mixture is then poured onto a substrate made of polyethylene terephthalate to form a thin layer (layer thickness about 15 μm).

It is as described in Example 1 in a sensitometer exposed behind a gray step wedge. The exposed material is then set for about half a second a water vapor atmosphere of about 50 °.

The layer is saturated with about 30 seconds for the formation of bubbles Treated hydrogen peroxide vapor at 70 ° and then exposed to a water vapor atmosphere of 75 ° for 1/2 second.

An image is obtained which has a density of 1.8 in directed white light.

Example 4

To 1 1 of 6 follow gelatin solution are added 25 cc of a 1 catalase. Then 50 ecm of a saturated solution of malachite green leukocyanide (Mtril of malachite green; cyanide releasing agent) are emulsified in ethyl acetate with vigorous mixing in the dark. It is then poured as described in Example 3 and processed further to form a bubble image.

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Claims (6)

Patent claims: Qy Process for the production of positive photographic images by imagewise exposure of a layer and subsequent treatment with a peroxide compound, characterized in that a photosensitive layer is used which contains in uniform distribution catalase-active or peroxidase-active ferments which are imagewise deactivated by exposure to actinic light. 2. The method according to claim 1, characterized in that a photosensitive layer is used, which in addition Contains sensitivity-increasing substances which, when exposed to light, release products that are catalase-active or deactivate peroxidase-active ferments. 3. The method according to claim 2, characterized in that a layer is used which contains compounds at Release halogen or gyanide from exposure. 4. Process according to claims 1-3, characterized in that that the exposed image with a peroxide compound is treated, which is decomposed on the ferments, which have remained active in terms of image, with the formation of oxygen and then the resulting gas is expanded by heating the layer to form a bubble image. 5. The method according to claim 1-4, characterized in that mixtures of mixtures to generate the bubble image Peroxides and hydrazines can be used. A-G 570 - 13 - 109820/1783 6. The method according to claims 1-3, characterized in that the exposed layer with peroxide compounds is treated in the presence of reaction components for a coloring oxidation reaction. A-G 570 - 14 - 109820/1783