DE1213241B - Process for the preparation of direct positive dye photographic images - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
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G 03 c

German class: 57 b -14/03

A 46672 IX a / 57 b July 24, 1964 March 24, 1966

The invention relates to a method of manufacture of photographic color direct positive images through the simultaneous use of amidrazones, which react with developer oxidation products to form stable, colorless end products, and Compounds which do not or under the conditions of the usual photographic processing only with the formation of colorless ones or those that become colorless in the course of the photographic process Compounds react with oxidized developers, preferably have no developer effect themselves and with an amidrazone under oxidizing conditions z. B. in usual photographic Bleach baths react to form dyes, with the processing of the exposed photographic material under otherwise normal conditions using a black-and-white or color developer is carried out.

The use of organic compounds, which react to form colored products under oxidation and which contain hydrazone moieties in photographic materials is known per se. There are for example in German Patent 1,083,125 dihydrazones of α, β-dicarbonyr compounds for Production of direct positive images described. These dihydrazones are practically colorless and become at the areas exposed to light in the course of color photographic processing by developer oxidation products also converted into colorless secondary products. When bleaching the silver image, use an oxidizing bath they converted into a yellow-orange colored substance in the unexposed areas. In this way colored direct positive images can be produced, but these are relatively weak in color. You are suitable for the production of color masks.

As such, a method of making color direct positive images would be like that in the foregoing German patent described principle compared to the known direct positive process extremely beneficial. Such a process would be equivalent to the known reversal films consider that the processing would be much easier, since the second exposure and the Second development would be superfluous.

In the Belgian patent specification 602 250, amidrazones of a certain constitution are used for production used by colored makeup images. These amidrazones have the property of having color couplers to couple oxidatively, so that after the color development in the bleaching bath on the unexposed and undeveloped areas a colored positive image Process of making photographic direct positive dye images

Applicant:

Agfa-Gevaert Aktiengesellschaft, Leverkusen, Kaiser-Wilhelm-Allee 24

Named as inventor:
Dr. Walter Püschel, Leverkusen; Dr. Karl-Wilhelm Schranz, Opladen; Dr. Wolfgang Lässig, Cologne-Stammheim; Dr. Hermann Marks, Cologne-Dellbrück; Dr. Hans-Heinrich Credner, Munich

arises. The principle of the reaction used there is described in an article by S. H ü η i g and F. M ü H e r, Annalen, 651 (1962), pp. 73 ff., Described. In the German Auslegeschrift 1 146 751 used this principle for the production of color direct positive images, the difference being in the Acid sensitivity of the customary color couplers due to the reaction with the oxidation products of customary color developers produced dyes and the oxidative coupling of the amidrazones and color couplers resulting dyes is used. The procedure is carried out in such a way that that first of all exposed, color-developed, bleached and fixed in the usual way, which is then followed a chemical treatment with a strongly acidic aqueous solution follows, which is what causes the color development so-called primary dyes are destroyed, while those caused by oxidative Coupling in the bleach bath so-called secondary dyes are retained. The great The disadvantage of this process is the acid treatment. This is the practical usability in Questioned because the differences between the dyes with regard to their sensitivity to acids are not so great are that some would be completely and irreversibly destroyed, while others in sufficient State.

609 539/390

In the German patent specification 1 195164 a process for the production of color direct positive images described, which is carried out much more easily can be compared to the processes known up to then. The main feature of this procedure is the use of amidrazones or their vinyl homologues, phenylene homologues or Azavinylene homologues that react with developer oxidation products to form colorless stable products react and their oxidation products with übli- ία Chen color couplers react to colored products ·. A certain implementation of the Procedure or materials constructed in a certain way ensure that no rs when developing the exposed material colored images occurs due to the reaction of the developer oxidation products with the usual color couplers which are also present. The latter are for that Process is also necessary, as it deals with the oxidation products of the bleaching bath Amidrazones react to form colored products with the formation of a direct positive image. By the The latter requirement is either the implementation of the process or the establishment of a suitable one Materials quite complicated.

The invention is based on the object of developing a color direct positive process that does not have the above disadvantages and easily produces color direct positive images excellent quality.

It has now been found that colored direct positive images according to the principle of the German patent 1 195 164 using the amidrazones described there in a surprisingly simple manner Way can be prepared if compounds are used in place of the usual color couplers which are preferably not or at most with the formation of colorless products with developer oxidation products react, which preferably themselves have no developer action and those with the Oxidation products of the amidrazones can be converted into colored compounds.

Aromatic amines such as aniline or naphthylamine have proven particularly suitable for this purpose or derivatives thereof. Substances that are a grouping of the following are useful Formula contain:

The phenyl ring of the general formula can be substituted in any way, with only care must be taken that either one of the two o-positions or the p-position to the amino group is unsubstituted or such substituents are contained in these positions, which under the conditions can be split off during processing. This includes, for example, SO3H.

The following are generally suitable as substituents: halogens such as chlorine or bromine, alkyl or alkoxy with up to 20 carbon atoms, carboxyl, carboxyl esters with preferably aliphatic alcohols up to 20 carbon atoms, Sulpho, sulphonamide or carbonamide, it being possible for the amide groups to be substituted by alkyl radicals up to 20 carbon atoms or acyl radicals, especially those which are derived from aliphatic carboxylic acids derive up to 20 carbon atoms, also nitro, nitrile or amino groups, the substitution in 0- or m-position is preferred, since the p-amino derivatives because of their often strong developer action are less suitable, the amino group can be substituted with alkyl up to 20 carbon atoms, acyl, in particular acyl, which is derived from aliphatic carboxylic acids with up to 20 carbon atoms, or phenyl; the phenyl ring of the above formula can also be replaced by further phenyl or naphthyl rings in a simple manner Wise substituted or contain these in fused form.

Since, of course, the substituents on the phenyl ring of the above formula are also substituted in turn can be, there are many possible variations, with certain properties such as Solubility or the color of the reaction product with the oxidized amidrazones is more advantageous Way can be modified. When selecting the substituents, it is only necessary to ensure that that the resulting products do not adversely affect the photographic properties of the material and under the usual photographic processing conditions with developers or their oxidation products do not react or at most react with the formation of colorless products. Compounds are preferred with substituents that make the molecule resistant to diffusion.

These compounds can be used in the form of the free amines or as salts of any acids will. These include, for example, the following connections:

55

Herein, R 'and R "mean the same or different can be hydrogen, alkyl up to 20 carbon atoms, aryl, in particular phenyl or naphthyl, Aralkyl such as benzyl or phenylethyl or heterocyclic radicals such as pyridine or quinoline.

The substituents R 'and R "can together form a heterocyclic ring, preferably a saturated ring such as morpholine, piperidine, pyrrolidine or piperazine. Along with of the o-methine group of the benzene ring, R 'and / or R "can also form heterocyclic rings. These include, for example, rings of the tetrahydroquinoline type.

HO ₃ S - (CH ₈ K / Ci ₂ H ₂₅

NH

HO ₃ S

0-Ci ₈ H;

18 * 137

IV

NH ₂

HOOC

NH - CO - Ci ₅ H ₃ I.

NH ₂

H
N-CH ₂

CH ₃

/ N-NH ₂

VIII

SO ₃ H

Ci ₂ H ₂₅

CH ₂ \

H ₂ C
H ₂ C

CH ₂
CH ₂

HCl

Ci ₂ H ₂₅

CH ₂ -CH ₂ OH

HN - (CH ₂ ) ₄ - SO ₃ H

XIII

XIV

Tertiary amines are preferably suitable for the process according to the invention. The manufacture of the. Amines are generally known per se. Other connections can be made in an analogous manner or according to other methods known to those of ordinary skill in the art.

So the diffusion-making radicals in the compounds I, X, XII and the pyrrolidinyl radical in connection XI by reacting the unsubstituted aromatic amines known per se with carry out the corresponding alkyl halides in a generally known manner. Also the introduction a diffusion-proofing radical in the compounds V, XIII is dem acylation reaction Well known to those of ordinary skill in the art. Finally, in connection III, the diffusion-proofing Remainder by reaction of the corresponding 1-acetaminophenol in the form of an alkali phenolate introduce with octadecyl bromide. The free amine is obtained by acidic or alkaline saponification.

The above amines are used in amounts of 1 to 120, preferably 15 to 70 g per mole of halosilver.

Other suitable connections can be determined by simple manual tests. Such Substances can have a wide variety of chemical structures, all that is required is the above specified properties must be present. These properties can e.g. B. stated as follows will:

Attempt 1

A few milligrams of the substances to be examined become in a few milliliters of aqueous alkali

(e.g. a soda solution) if necessary with the addition of a solubilizer (e.g. methanol) and the solution with a few milligrams of a photographic developer (e.g. 4-diethylaminoaniline) offset. Then with an oxidizing agent (e.g. an aqueous solution of potassium persulfate) treated.

In this case, the substances to be examined react with the developer oxidation product there is no stable colored connection. In this context it must be noted that the developer can react with the oxidizing agent to form unstable dark decomposition products. These are but irrelevant.

Attempt 2

A few milligrams of the substance to be examined are dissolved in a suitable solvent, z. B. methanol, dissolved and the solution buffered, e.g. B. by adding an aqueous sodium acetate solution. An amidrazone is then added according to the method according to the invention, e.g. B. Amidrazone 1. Now a 5% potassium ferricyanide solution, as is usually also found in Bleach baths used are oxidized. In this case, a stable colored connection must go through The compounds to be investigated react with the oxidation product of the amidrazone.

As amidrazones, their oxidation products to form colored compounds by reaction with the above aminophenyl or aminonaphthyl derivatives must be capable, in particular are in the German patent specification 1 195 164 mentioned suitable. Amidrazones are general Understand connections that make up the grouping

\ γ C = N N

contain. Vinylene homologues, phenylene homologues or azavinylene homologues are those used in the above Formula between the carbon atom and the amine grouping a vinylene grouping, one Contain phenylene radical or an azomethine group. Such amidrazones are in the Belgian patent 602 250 or the German Auslegeschrift 1 146 751. Connections are useful of the following general formula:

wherein Y represents a chemical bond, a vinylene grouping, an azomethine grouping or a phenylene group; X represents alkyl such as methyl, ethyl, butyl, hexyl, palmityl or stearyl, olefinically unsaturated alkyl such as allyl, aryl, preferably phenyl or naphthyl, aralkyl such as benzyl or phenylethyl or cycloalkyl such as cyclohexyl; the above groups, preferably the phenyl radicals, can in turn be substituted, for example with halogen such as chlorine or bromine, alkyl such as methyl or ethyl with preferably up to 5 carbon atoms, hydroxyl, alkoxy such as methoxy, ethoxy, carboxyl, carboxy ester, amino, acylamino such as acetylamino or stearoylamino, alkylamino, sulfo, aminosulfonyl, esterified sulfo groups, alkylsulfonyl or the like; Ri can mean hydrogen, alkyl with up to 20 carbon atoms such as methyl, ethyl, butyl, stearyl, olefinically unsaturated alkyl such as allyl, cycloalkyl such as cyclohexyl, aryl, preferably phenyl or naphthyl, or aralkyl such as benzyl or phenylethyl, the above groups preferably the phenyl radicals themselves can be substituted, for example with halogen such as chlorine or bromine, alkyl such as methyl or ethyl with preferably up to 5 carbon atoms, hydroxy, alkoxy such as methoxy, ethoxy, carboxy ester, amino, acylamino such as acetylamino or stearylamino, alkylamino, · Sulfo, aminosulfonyl, esterified sulfo groups, alkylsulfonyl or the like; R ₂ can mean hydrogen, alkyl with up to 20 carbon atoms such as methyl, ethyl, butyl, stearyl, olefinically unsaturated alkyl such as allyl, cycloalkyl such as cyclohexyl, aryl, preferably phenyl or naphthyl, or aralkyl such as benzyl or phenylethyl, the above Groups, preferably the phenyl radicals, can in turn be substituted, for example with halogen such as chlorine or bromine, alkyl such as methyl or ethyl with preferably up to 5 carbon atoms, hydroxy, alkoxy such as methoxy, ethoxy, carboxyl, carboxy ester, amino, acylamino such as acetylamino or stearylamino, alkylamino, sulfo, aminosulfonyl, esterified sulfo groups, alkylsulfonyl or the like; Those substituents which have a diffusion-resistant or water-solubilizing effect are preferred. X and Ri and / or R2 together can also represent the methylene or methine groups or heteroatoms such as O, S, Se or ^ required to complete a simple or fused 5- or 6-membered heterocyclic ring; the combination X + Ri can mean, for example, the following heterocycles: oxazole, benzoxazole, thiazole, benzthiazole, selenazole, benzselenazole, imidazole, benzimidazole, pyrrolidone, quinoline, piperidine, pyrimidine; the combination X + R2 can mean piperidine, morpholine, pyrazole, pyrazoline, pyrrolidine, oxazolidine. R3 denotes hydrogen, acyl such as acetyl, stearoyl, palmitoyl or a carbonamide group which can be substituted by alkyl or aryl; R4 is hydrogen, * a sulfo group, aminosulfonyl, alkylsulfonyl such as methylsulfonyl, ethylsulfonyl or Stearylsulfonyl, arylsulfonyl such as phenylsulfonyl or naphthylsulfonyl, aminosulfonyl which may be substituted with alkyl or phenyl ^{st '0 <^ he e} * ^ne sulfonyl group bonded to a heterocyclic system is, or carbonamide; the above groups, preferably the phenyl radicals, can in turn be substituted, for example with halogen such as chlorine or bromine, alkyl such as methyl or ethyl with preferably up to 5 carbon atoms, hydroxy, alkoxy such as methoxy, ethoxy, carboxyl, carboxy ester, amino, acylamino such as acetylamine or stearoylamino, alkylamino, sulfo, aminosulfonyl, esterified sulfo groups, alkylsulfonyl or the like; Those substituents which have a diffusion-proofing effect are preferred. R ₃ and R 4 together can represent the remainder of an aliphatic saturated or unsaturated 1,2- or 1,3- or an aromatic o-dicarboxylic acid with formation of a 5- or 6-membered heterocyclic ring, for example the maleimide ring, the succinimide ring, glutaric acid imide ring or phthalimide ring.

The amidrazones are generally known

Process made. Useful methods are described in the patents cited above.

The following amidrazones are specifically noted:

/ uniurdzon

N - SO2 - ■ C18H37

20 g of N-ethyl-benzthiazolone hydrazone, 35 g of octadecylsulfonyl chloride and 8 g of pyridine in 600 ecm of acetonitrile are refluxed for 2 hours. On cooling, 39 g (69.1% of the

10

Theory) 3 - ethyl - 2 - benzthiazolone - β - octadecylsulfonylhydrazone with a melting point of 11 to 114 ° C.

Amidrazone

N-NH-

NH - CO - CH - CH - CH ₂ - CH

15 g of a vinylpyrrolidone maleinsäureanhydridmischpolymerisates (see FIG. German Auslegeschrift 1,123,913) are dissolved at 90 to 100 ⁰ C in 100 cc of glacial acetic acid. 20 g of 3-aminophenyl-sulfqnylhydrazqn of N-ethylbenzthiazolone-2, dissolved in 200 ecm of dimethylformamide, are added to this solution.

The mixture is then kept at 100 ° C. for 1 hour and then water is discharged to 41%, filtered off with suction and dried at normal temperature in a vacuum. Yield 30g. Connections 3 and 4 produce.

3.

N-NH-SQ ₂

NH - CO - CH - CH - CH ₂ - CH—

OH

H ₂ C CH ₂

4th

H ₂

NH - CO - CH - CH - CH ₂ - CH -

C = N-NH-SO ₂

C = O / NH ₂ C

OH

H ₂ C-

-CH ₂

The amidrazones are added to the halogen emulsion in amounts of 1 to 120, preferably 15 to 70 g added per mole of halosilver at any stage in the preparation of the emulsion, preferably nacii of chemical ripening before potting.

The usual processing baths are suitable for carrying out the process according to the invention. for example the following:

55 A. Developers

The developers can be composed in the usual way be. It is advantageous to match the developer to the amidrazone used, which can be achieved by a few simple experiments.

1. 4-Amino-N, N-diethylaniline sulfate ... 2.5 g

Sodium sulfite (sicc.) 1.0 g

Potassium bromide 1.0 g

Potassium carbonate 75.0 g

Water 11

In the following developers this is 4-amino-N, N-diethylaniline sulfate replaced by:

2. 4-Amino-N, N-butylbutanesulfoaniline 5.0 g

3. p-amin.ophenol 5.0 g

4. p-methylaminophenol 5.0 g

5. Glycine 15 g

6. 1-phenyl-pyrazolidone-3 3 g

7. 4-amine, ophenimine 5 g

8. Hydroquinone. 5 g

9. catechol 5 g

B. bleach bath

In principle, the usual bleach baths or bleach-fix baths can be used, for example aqueous ones Solutions of complexes of trivalent iron or trivalent cobalt with aminopolycarboxylic acids, such as Ethylenediamine tetraacetic acid or aqueous solutions of potassium dichromate, potassium ferricyanide or the like. About 20% solutions are useful, for example a 20% aqueous solution of potassium

609 539/390

ferricyanide. The bleach baths can be made by adding alkalis or acids to the desired pH value can be brought.

D. Fixing bath

The usual baths can be used for fixing the materials described, for example Thiosulfate solutions, such as a 20% aqueous sodium thiosulfate solution.

Other conventional photographic processing baths can also be used. You are though Basically irrelevant for the procedure, but can be advantageous in some cases. For this belong e.g. B. stop baths, which can have a pH value down to 3, or hardening baths etc.

Silver chloride or silver bromide can be used as silver halides for the light-sensitive emulsions possibly with a few mole percent silver iodide or mixtures thereof can be used.

The usual hydrophilic colloids are suitable as binders, such as preferably gelatin, the but in whole or in part by products such as carboxymethyl cellulose, polyvinyl alcohol, alginic acid or their derivatives, such as salts, esters or amides, can be replaced;

The layers can be optically or chemically sensitized in the usual way. You know you can Contains stabilizers, wetting agents, etc.

The amidrazones or the aromatic amines used in the manner according to the invention can diffusion-resistant in dissolved or emulsified form the photographic layers, especially the light-sensitive silver halide emulsion layers.

However, the aromatic amines can also be used according to the known development process being used between the developer and the bleach bath To be added to the bath itself.

The method of the invention is useful for producing both monochrome and multicolor direct positive images suitable. The first-mentioned monochrome pictures can act as masks. In the case of so-called built-in masks, the color images themselves can then be converted into conventional Way to be made. For the production of multicolor photographic images, photographic Multilayer materials are used which contain light-sensitive layers in the usual way, which are sensitive to the three primary colors of the spectrum. The multicolor images are generated according to the known subtractive principle.

For example 1 1

A 1.0 g of the amine I and 1.0 g of 2 Amidrazins to 100 ml containing silver emulsion is applied to a suitable substrate, exposed and developed for 5 minutes at 2O ⁰ C in the following developer:

4-Amino-N, N-butylbutanesulfoaniline 5.0 g

Sodium sulfite (sicc.) 1.0 g

Potassium bromide ..: 1.0 g

Potassium carbonate 75.0 g

Water 11

Then it is bleached and fixed in the usual way. A purple, positive image is obtained.

Example 2

In the material given in Example 1, amine I is replaced by amine II and the resulting Material processed as described in Example 1. A blue, positive image is obtained.

By using other aromatic amines

ίο you can get different colored pictures. The one in the The amines given in the following table give images of those given below with the same processing Colours.

15th Amine colour X violet XI Blue violet XII blue 20th XIII blue XIV violet

Example 3

• 25 is replaced in example 1 while maintaining the • ■ · ■ rest of the approach and the processing conditions Amine I through amine III results in a red, positive image.

Example 4

Replaced in Example 1 while maintaining the remainder of the batch and the processing conditions Amine I through amine IV, a blue, positive image is obtained.

Example 5

Replaced in Example 1 while maintaining the remainder of the batch and the processing conditions Amine I through amine V, you get a red, positive image.

Example 6

Replaced in Example 1 while maintaining the remainder of the batch and the processing conditions Amine I through amine VI results in a purple, positive image.

Example 7

If the material described in example 2 is not processed in a color developer according to example 1, but uses a methylaminophenol developer, e.g. B. receives the developer A 4 you also get a blue, positive image.

Example 8

In a corresponding way, you get a blue, positive image if you use the developer in the example by an aminophenol developer, e.g. B. the developer A 3 replaced.

Claims (4)

Patent claims: 1. A method for preparing direct positive dye photographic images using a photographic light-sensitive material comprising at least one halide silver emulsion layer contains, characterized by a) imagewise exposure of a photographic material comprising at least one halide silver emulsion layer contains, in the amidrazones or vinylene homologues, their phenyl homologues or azavinylene homologues are embedded b) development with a photographic developer, c) bleaching with an oxidizing bleach bath and d) fixation by methods known per se, the oxidative bleaching in the presence of organic compounds (in particular aromatic amines) which do not or only form colorless products or those products that become colorless in the course of the photographic processing, react with developer oxidation products, which preferably have no development effect themselves and who deal with the oxidation convert products of the amidrazones into colored compounds. 2. The method according to claim 1, characterized in that the oxidizing bleaching in The presence of aniline or naphthylamine or derivatives thereof is carried out. 3. The method according to claim 1, characterized in that aniline or naphthylamine or derivatives thereof in diffusion-proof form in the halogen silver emulsion layer, which also contains the amidrazones or their vinylene homologues, phenylene homologues or azavinylene homologues, are embedded. 4. Photographic light-sensitive material for the production of direct positive dye images with at least one photosensitive halogen silver emulsion layer for the process according to claims 1 to 3, characterized by a content of amidrazones or their Vinylene homologues, phenylene homologues or azavinylene homologues, aniline, naphthylamine or Derivatives thereof. 609 539/390 3.66 © Bundesdruckerei Berlin