DE1195164B - Process for the preparation of direct positive color photographic images - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

G 03 c

German KL: 57 b - 18/13

1 195 164
A 45551IX a / 57 b
March 20, 1964
June 16, 1965

The invention relates to a method of manufacture of color direct positive photographic images through the simultaneous use of conventional color couplers and monohydrazone compounds that interact with the oxidation products of developing agents React to colorless stable end products and those with color couplers under oxidizing conditions react to form dyes, the production of the colored positive image being carried out in this way becomes that during the development of the exposed material no color image due to the reaction of a color coupler with developer oxidation products.

The use of organic compounds associated with the oxidation products of color couplers react and which contain hydrazone groups in photographic materials is known per se. There are, for example, in German Patent 1,083,125 dihydrazones of α, / 5-dicarbonyl compounds for the production of direct positive images. These dihydrazones are practically colorless and are carried out at the light-struck areas in the course of color photographic processing the developer oxidation products converted to likewise colorless secondary products. When fading of the silver image by means of an oxidizing bath, they become closed at the unexposed areas a yellow-orange colored substance implemented. In this way, colored direct positive images can be produced which are relatively weak in color. They are suitable for the production of color masks. At would be a method for producing color direct positive images according to that in the above German patent described principle compared to the known Direktpositiwerfahren extraordinary advantageous. Such a process would be superior to the known reversal films in that 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 development of the color in the bleaching bath on the unexposed and undeveloped areas create a colored positive image. The principle of the reaction used there is described in an article by S. H ü η i g and F. M ü Iler, Annalen, 651 (1962), pp. 73 ff.

In the German Auslegeschrift 1 146 751 this principle for the production of colored direct method for the production of direct positive
color photographic images

Applicant:

Agfa Aktiengesellschaft,

Leverkusen, Kaiser-Wilhelm-Allee 24

Named as inventor:

Dr. Walter Püschel, Leverkusen;

Dr. Karl-Wilhelm Schranz, Opladen

used 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 method is carried out so that first is exposed in the usual way, color developed, bleached and fixed, whereupon a chemical Treatment with a strongly acidic aqueous solution follows, which is the result of the color development so-called primary dyes are destroyed, while those are destroyed by oxidative coupling in the bleaching bath so-called secondary dyes formed are retained. The big disadvantage of this procedure is the acid treatment. This calls into question the practical usability, since the differences of the dyes, with regard to their acid sensitivity, is not so great that some completely and would be irreversibly destroyed while the others would remain in sufficient condition.

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

According to the invention, a property of amidrazones or vinylene homologues becomes phenylene homologues or amidrazones homologous to azavinylene in the Belgian patent specification 602 250 and German Auslegeschrift 1 146 751 described type exploited, which has been overlooked by the professional world and which consists in that this amidrazones with the oxidation products of common developers, both from color developers and

509 580/331

black and white developers also react to form colorless products that react to oxidizing agents, as used in photographic bleaching baths are stable.

The image produced by the process according to the invention consists of azo or azine dyes of the same type as the dyes produced according to the German Auslegeschrift 1,146,751. The inventive The method is characterized in principle in that the production of the direct · ο positive image is carried out so that a formation of negative color images by reaction of the customary color couplers with the oxidation products of a color developer are avoided at all.

For this purpose, the following special execution «5 shapes possible:

1. The photosensitive Halpgen calf emulsion layer contains amidrazones or vinylene homologues, phenylene homologues or azavinylene homologues Amidrazones. It is imagewise exposed and developed so that the amidrazones imagewise are converted into colorless stable products at the exposed areas. The usual Color couplers are then treated with a solution, the color couplers contains, introduced into the layers and oxidative during the bleaching with the amidrazone system coupled. According to a preferred embodiment, the color coupler can also be the Bleach bath can be added. This process variant is similar in its technical Executions of the so-called development process.

2. The halogen silver layer contains the amidrazones or vinylene homologues as indicated under 1, phenylene homologues or azavinylene homologues and amidrazones in an adjacent one The usual color couplers are embedded in a halogen-silver-free layer in a diffusion-proof form. The amidrazones used are those which are resistant to diffusion, their oxidation products However, when they are oxidized in the bleaching bath, they become diffusible, so that they enter the neighboring Color coupler containing layer can migrate and there with the color coupler to one Dye can react.

This embodiment can, like embodiment 1, by using a Multilayer photographic material for the production of multicolor images, preferably can be used according to the subtractive principle.

3. According to the simplest embodiment of the method according to the invention, such photographic materials used in photosensitive silver halide emulsion layers in effective contact both the color couplers and the amidrazones or vinylene homologues, phenylene homologues or azavinylene homologues Amidrazones included. The exposed material is in a black and white developer developed whose oxidation products are indeed with the amidrazone or the vinylene homologue, phenylene homologue or azavinylene homologue Amidrazone to colorless Pro- <> s but do not react with the color coupler. In the bleach bath you get by oxidative Coupling a positive colored picture.

Amidrazones are generally understood to mean compounds which have the grouping

contain. Vinylene homologues, phenylene homologues or azavinylene homologues are those used in the above Formula between the carbon atom and the amine group is a vinyl group, a phenylene radical or contain an azomethine group.

The methods according to the invention are essentially as described in the Belgian patent 602250 or the Amidrazone described in German Auslegeschrift 1 146 751 are suitable. Such connections fall under the following general formula

Ri-

Λ {

C =
Y

/ RT \
W.

τ /

wherein Y is a chemical bond, a vinylene grouping, an azomethine grouping or a Denotes phenylene group; X stands for 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, hydroxy, alkoxy such as methoxy, ethoxy, Carboxyl, carboxy ester, amino, acylamino such as acetylamino or stearoylamino, alkylamino, sulfo, Aminosulfonyl, esterified sulfo groups, alkylsulfonyl od. Ä; 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 being preferred the phenyl radicals, in turn, 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, carboxyl, carboxy ester, amino, acylamino such as acetylamino or stearylamino, Alkylamino, sulfo. Aminosulfonyl, esterified sulfo groups, alkylsulfonyl or the like; R2 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, where the above groups are preferably the phenyl radicals for their part may 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,

5 6

Carboxyester, Amino, Acylamino such as Acetylamino winder can be used. It is also beneficial

or stearylamino. Alkylamino, sulfo, aminosulfur, the developer to the amidrazone used

fonyl, esterified sulfo groups, alkylsulfonyl or the like; tune what through a few simple attempts

those substituents which can be reached are preferred.

a diffusion-resistant or water-solubilizing «,. . . , _{T xT} , -. ,, ... _1C . -, £.

Have an effect. X and R ₁ and / or X and R ₂ to- " ^L 4-Ammo-N N-diethylamine sulfate .. 2.5 g

The wauiumsuint ^ sicc; ι, υ g

of a simple or fused five or six-membered £ * i ^um ^ " _t -i'Ji ^g

heterocyclic ring required methylene WassS 11 ^S

or methine groups or heteroatoms such as O, S, Se io

or N; the combination X _T Ri can In the following developers the 4-amino-

z. B. mean the following heterocycles: Oxazole, N, N-diethylaniline sulfate replaced by:

Benzoxazole, Thiazole ^ Benzthiazole Selenazole Benz- ₂ 4-Amino-N, N-butylbutanesulfoaniline 5.0 g

selenazole, imidazole, benzimidazole, pyrrolidone, Chmo- -i λ \ ■ u ι ^ n

lin, piperidine, pyrimidine; the combination X + R ₂ .s / l ~ t ^ X ™? J? Lh ^ In

can mean piperidine, morpholine, pyrazole, pyr- " ^A , g-methylammophenol 5.0 g

azoline, pyrrolidine, oxaazolidine. /, 4, ";.Y" ~ \ ^>

Rhombus hydrogen; Acyl such as Ace «y>, Stearoy, \% ££% * ??. \ \ \ \ \ \ \ \ \ \ \ If

Palmitoyl or a carbonamide group with _R ΐΓνΛτγνΤιίηηη s %

Alkyl or aryl may be substituted; R ₄ stands for 20 q £ ^y * w « «

Hydrogen, a sulfo group, aminosulfonyl, alkyl ^{y ßrenzcarecmn} ■ · ■ ³ S

sulfonyl such as methylsulfonyl, ethylsulfonyl or _ß z _w i _sc henbäder stearylsulfonyl, arylsulfonyl such as phenylsulfonyl or

Naphthylsulfonyl, aminosulfonyl, which is substituted with alkyl or the following intermediate baths are used for the phenyl, or a sulfonyl group, which can be carried out in process variant 1. A heterocyclic system can be attached, or the usual color couplers can be used. Carbonamide; The above groups, preferably the phenyl radicals in the processing of multilayer materials, can in turn be substituted; 30 only the desired layer reacts. Here, 5 carbon atoms, hydroxy, alkoxy such as methoxy, can be used in the known technology in the one-development ethoxy, carboxyl, carboxy ester, amino, acylamino process, such as acetylamino or stearoylamino, alkylamino,. _T .., sulfo, aminosulfonyl, esterified sulfo groups, alkyl ¹ · ¹⁰⁰ ^ g? ^wa _c ^ßn p solution TOnl-phenyl-3-methylsulfonyl or the like; Preferred are those sub-, 5-parazolon-5 that are obtained by adding 2 n-sodium substituents. a diffusion-preventing effect ' ^"1 ™ & ^{tel e} J ^NEM pH of 8 in demeanor solution ^{is introduced..} -

Rs and R4 together can be the remainder of an ali- 2.3% aqueous solution of 1-naphtholsulfone

Phatic saturated or unsaturated 1,2- or acid-4, which can be obtained by adding 2N sodium hydroxide solution

1,3- or an aromatic o-dicarboxylic acid below 40 at a pH of 8 in solution

Formation of a 5- or 6-membered heterocyclic is.

Represent ring, for example the maleic acid 3 _{30 / i wäßri Lö yon} ! _ _{ΡΙιεηγ1αΐη} ί _ηο .

imidnng the Succimmidring, Glutarsaureimidnng naphthalene-sulfonic acid-8, which by adding

or Phthahmidnng. of 2 η sodium hydroxide solution at a pH value of 8

_Is in the oxidation of compounds of the above 45 _{lacked in solution} f. general formula, the substituents R3
and Pv4 split off. When choosing suitable

Amidrazone for the three above-mentioned forms of C. Bleaching bath should be taken into account. So can with that

Process where the diffusion resistance is increased by the Oxy- 50 In principle, the usual bleach baths or

dation of the amidrazone is to be eliminated as useful in bleach-fix baths, for example aqueous ones

the embodiment (2), only such amidrazones solutions of complexes of trivalent iron or

or their vinylene homologues, azavinylene homologues of trivalent cobalt with aminopolycarboxylic acids, such as

or phenylene homologs are used, which only contain ethylenediaminetetraacetic acid or aqueous solutions

in the removable substituents, these are R3 and 55 of potassium dichromate, potassium ferricyanide or the like.

Ri, have long aliphatic residues. In the group are usable about 20% solutions, for example

pen Ri and Ra should any alkyl present a 20% aqueous solution of potassium ferricyanide.

residues do not have more than 6 carbon atoms. The bleaching baths can by adding alkalis

preferably about 1 to 3 or acids brought to the desired pH

For the implementation of the 00 according to the invention are.

Process are the usual processing baths ^ p. - "^" j suitable, for example the following:

AFt 'ckl ^ " ^r ^' ^e Fi ^x i ^erun g the materials described

the usual baths are useful, for example

The developers can be composed of thiosulphate solutions in the usual way, such as a 20% aqueous name being only in the selection of the trium thiosulfate solution.

Developing substance must be taken care of, It can also use other, conventional photographic

that in the embodiment (3) black and white treatment baths are used up. You are though

IO

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 and the like.

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 usual color couplers can be used for the oxidative coupling with the amidrazone, for example of the / S-ketoanilide type, phenols or naphthols, pyrazolones, indazolones, products with cyanoacetyl groups or pyrazolobenzimidazoles.

Production of the amidrazones described

The sulfonylhydrazones used are prepared according to generally known methods manufactured. The linkage with diffusion-proofing residues takes place in the following way:

Connection 1

H
N-N-SO ₂ -Ci ₈ H ₃₇

C ₂ H ₅

20 g of N-ethylbenzthiazolonhydrazone, 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 theory) of 3-ethyl-2-benzthiazolone- β- jn-octadecylsulfonylhydrazone with a melting point of 111 ° to 114 ° C. crystallize out.

link

NH - CO - CH - CH - CH ₂ - CH -
\ C = O / N

OH

Alkyl

/ N \

T I

H ₂ H ₂

15 g of a vinyl pyrrolidone-maleic anhydride interpolymer (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-aminophenylsulfonylhydrazone 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 discharged into 41% of water, filtered off with suction and dried at normal temperature in a vacuum. Yield: 30 g.

Connections 3 and 4 can be made in the same way.

N-NH-SO ₂

NH - CO - CH - CH - CH ₂

H ₂ - H ₂

C = N-NH-

CH ₃

NH - CO - CH - CH - CH ₂ - CH -

I I

C = O / N _x

OH ψ I

H ₂ -H ₂

A 1.5 g of compound 1 on the ECM 100 containing silver emulsion is applied to a suitable support (e.g., as a film on acetyl cellulose, polycarbonate, or polyethylene terephthalate), exposed and developed for 5 minutes at 20 ⁰ C in the developer A 1. After an intermediate wash of 15 minutes, one of the intermediate

baths B 1 to B 3 are switched on for 2 minutes and then in baths C and D. bleached and fixed. If the intermediate bath B 1 is used, a yellow one is obtained, and B 2 a red one and a blue, directly positive image of B 3. s

The above material can also be used while maintaining the other processing conditions in the developers 2 to 9 can be developed. In all cases, the intermediate baths selected are obtained yellow, red or blue, directly positive images,

Example 2

The following photographic layers are applied to a film base in the order given applied:

1. A gelatin layer, produced with a casting solution containing 5% gelatin solution per 100 ecm Contains 4 g of 4-sulfo-1-naphthol-2-carboxylic acid stearyl anilide.

2. A blue-sensitive silver bromide emulsion, in which 9 grams per kilogram of emulsion of the compound 3 have been stored.

If you develop in developer 3, compound 3 couples in layer 2 at the exposed areas with the oxidized developer to compounds that are colorless or during the development process turn into colorless compounds. You can also use it in the subsequent bleaching process can no longer be oxidized to a coupling product. In the unexposed areas compound 3 is converted into a couplable form during the bleaching process, which is found in layer 1 diffuses and there couples with the existing component to form a dye. One receives on in this way a directly positive, red image of the exposed original.

Example 3

40

If the naphthol coupler in layer 1 of Example 2 is replaced by 1- (4'-sulfophenyl) -3-palmitylpyrazolone-5 and in layer 2 connection 3 through connection 2 and processes this layer analogous to example 2 with developer 2, then a directly positive, yellow image is obtained.

Example 4

If you replace the naphthol coupler in layer 1 of Example 2 with 1-naphtholcarboxylic _acid-SQ 2- (2'-N-stearyl-N-methylamine-4'-sulfoaniIid) and in layer 2 the compound 3 with compound 4 and works as in Example 2 given, but with developer 2. Then a directly positive, blue image is obtained. _ss

Example 5

One 1.0 g of Compound 2 and 1.0 g of the compound of the following formula

to 100 cc containing silver emulsion is applied on a suitable support, exposed, developed minutes at 20 ⁰ C in the developer 4, and then bleached in the baths C and D and fixed. A yellow, directly positive image is obtained.

Example 6

The material described in Example 5 is obtained while maintaining the other processing conditions developed in the developer 5. Here, too, you get a yellow, positive image.

Example 7

In the material described in Example 5, the coupler is replaced by the compound 4-sulfol-naphthol-2-carboxylic acid stearyl anilide. It is exposed, developed for 5 minutes at 20 ^° C. in developer 3 and then bleached and fixed in baths C and D. A red, directly positive image is obtained.

The above material is processed while maintaining the remaining processing conditions in the developers 6, 8 and 9 developed. In all cases you get a red, directly positive image.

Claims (5)

Patent claims: 1. Method of making direct positive color photographic images using a photographic light-sensitive material comprising at least one halide silver emulsion layer contains, indicated by a) imagewise exposure of a photographic material comprising at least one halide silver emulsion layer contains, in the amidrazones or their vinylene homologues, phenylene homologues or azavinylene homologues that are embedded with the oxidation products of photographic black and white or color developing agents colorless products react and which under oxidative conditions in the presence of Color couplers react to colored compounds, b) development with a photographic developer, c) bleaching with an oxidizing bleach bath and d) fixation, wherein the oxidizing bleaching is carried out in the presence of a color coupler and wherein the color couplers are arranged or the development is carried out so that they are at the development of the exposed material with color developer oxidation products does not can react to a color image. 2. The method according to claim 1, characterized in that the color coupler in diffusion-resistant Form in the halogen silver emulsion layer, which also contains the amidrazones or their vinylene homologues, Phenylene homologs or azavinylene homologs contains, is embedded, and that the exposed photographic material with a Black and white developer is developed whose 50 »580/331 Oxidation products do not react with the color coupler. 3. The method according to claim 1, characterized in that the color coupler is not in one light-sensitive, halogen-silver-free layer is embedded in a diffusion-proof manner, that of the light-sensitive Halogen silver emulsion layer containing the amidrazone, is adjacent, such amidrazone or their vinylene homologues, Phenylene homologs or azavinylene homologs are used, which are in diffusion-resistant form in the Halide silver emulsion layer are included, but from which, however, upon oxidation in the bleach bath the substituents that cause the diffusion resistance are split off so far that the Oxidation products of these amidrazones become diffusible. 4. The method according to claim 1, characterized in that a photosensitive photographic Material is used which does not contain a color coupler and which one after exposure and development before or during the oxidative bleaching treated with a solution of a diffusible color coupler in such a way, that it penetrates so far into the layer that it is there later or at the same time as the one at the Oxidation product of the amidrazone formed by reaction with the oxidative bleaching bath or their vinylene homologues, phenylene homologues or azavinylene homologues to a dye can react. 5. Process according to claims 1 to 4, characterized in that the amidrazones are those the following formula can be used wherein Y represents a chemical bond, a vinylene grouping, an azomethine grouping or a phenylene group; X is saturated or unsaturated alkyl, aryl, aralkyl, or cycloalkyl; Ri is hydrogen, saturated or unsaturated alkyl, cycloalkyl, aryl or aralkyl; R _{2 is} hydrogen, saturated or unsaturated alkyl, cycloalkyl. Aryl or aralkyl; X and Ri and / or X and R ₂ together can also denote the methylene or methine groups or heteroatoms required to complete a simple or fused 5- or ole-membered heterocyclic ring; R3 hydrogen. Acyl or a carbonamide group; Rj is hydrogen, a sulfo group. an aminosulfonyl group. Alkylsulfonyl, arylsulfonyl or a sulfonyl group bonded to a heterocyclic system, or carbonamide; R3 and R4 together can represent the remainder of an aliphatic saturated or unsaturated 1,2- or 1,3- or an aromatic o-dicarboxylic acid with the formation of a 5- or 6-membered heterocyclic ring.