DE1265580B - Process for making azo dyes diffusible in photographic gelatin layers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

G 03 c

Int. CL:

German class:

Number: 1 265 580

File number: A 46855 IX a / 57 b

Filing date: August 14, 1964

Open date: April 4, 1968

The invention relates to a method for producing colored photographic gelatin layers, in which reactive groups of azo dyes are bonded to gelatine in a diffusion-proof manner.

It is known to produce color photographic images by the silver dye bleaching process. This is done in a homogeneously colored colloid layer in the places where there was previously a silver image was produced photographically, the dye, mostly an azo dye, in a strongly acidic bath image-wise bleached.

Both negative and reversal images can be produced using this process. Do you want To achieve positive paper images or duplicate positives directly from slides, it is easier to work with Black and white development to create the silver image, which is then a negative of the master copy represents. Because the layer (or the three layers of a multicolor material) is homogeneous distributed image dye is destroyed in accordance with the silver image, the end result is that desired dye image positive for the original (reverse image). If one generates a positive one for the submission Silver image (silver reversal image), e.g. B. by a black and white reversal development or on the By way of the bromine ion diffusion process, after the color bleaching a template is created in the Gradation opposing dye image, d. H. a positive color image if the original is a color negative represents.

The requirements placed on dyes for the process described are special high, as these not only have to be spectrally suitable, but also have high fastness properties (especially Lightfastness) should also have good bleachability. You may also use the photographic Emulsion does not adversely affect and must be in the gelatin, which is almost exclusively is used as a layer former, be completely diffusion-resistant. Just a lack of diffusion resistance but represents one of the main difficulties for the use of many per se suitable dyes in Silver dye bleaching process. A number of Proposals have been made, especially the "pickling" of acidic dyes with the help of organic ones Bases such as B. Diphenyl-4,4'-dibiguanid according to French patent specification 864 332 or a definition the image dyes usually bearing sulfone groups are the same as basic dyes or a similar shade according to German patent specification 557 149. However, with these methods

Method for making
Azo dyes in photographic
Gelatin layers

Applicant:

Agfa-Gevaert Aktiengesellschaft,

5090 Leverkusen, Kaiser-Wilhelm-Allee 24

Named as inventor:

Dr. Bernhard Seidel, 5000 Cologne-Mülheim;

Dr. Edgar Siegel, 5090 Leverkusen-Steinbüchel; Dr. Klaus Sasse, 5000 Cologne-Stammheim

associated significant disadvantages, in particular a decrease in sensitivity. Diffusion-resistant polymers Azo dyes such as those described in British Patent 682,665 are not brilliant enough, and dyes attached to polymeric chains such as polystyrene, etc., like For example, in US Pat. No. 2,644,753, are difficult to convert into water-soluble Introduce colloid layers.

To circumvent the difficulties mentioned is in the Belgian patent 615 313 already have been described, dyes, in particular a mono- or dichlorotriazinyl radical of the formula

Cl

(X = Cl, alkoxy, F = dye residue), set to be reactive to gelatin. A similar Process, especially for the production of flake emulsions, is also in the Belgian patent 604 859 specified. It is known that the triazinyl radical, even after hydrolysis of the halogen atoms, the overall molecule gives a relatively high degree of substantivity to cellulose and therefore unreacted or hydrolyzed triazinyl reac-

809 537/531

It is usually difficult to wash out active dyes. It has been shown that the same difficulties also occur with gelatine and that here too the unreacted residues are hardly washed out permit. These non-hydrolyzed residues are not diffusion-resistant and can therefore affect the color balance affect the photographic material by diffusion. They can do a lot small amounts interfere considerably, because already very

The azo dyes used according to the invention also have a higher resistance to hydrolysis (before the reaction) than dichlorotriazinyl dyes, as a result of which a high percentage of intact reactive dye can be reacted more easily with the gelatin. The conversion with the gelatin takes place in the form that a concentrated gelatin solution (20% in water) at 45 to 50 ⁰ C at a pH value of 10 to 13, preferably at

small color densities the purity of image whites io 11 ^ 5, with a concentrated aqueous solution of the can cause considerable damage. Reactive dye implemented for about 30 minutes

It is also known that vinylsulphone groups are used.

containing reactive dyes with very good fixing properties. In this way, a

Let the hives attach to gelatine. In this stained gelatin obtained after rinsing In the case of the fixation reaction, however, strongly pH 15, it is exclusively reactive bound to the substrate addicted. This results in the practical application containing dye.

to considerable difficulties, so that this dye gelatins produced in this way

Fixation principle of limited importance in are suitable after mixing with photographic this context is. Emulsions of a suitable nature are excellent for producing

The invention is based on the object of making image layers for silver dye bleach diffusion resistant of azo dyes in photographic processes. Dyes can be used here, graphic gelatin layers a process to which is characterized by particularly high brilliance and spectral develop, which are characterized by a high diffusion resistance of the purity with good bleachability. the Dyes ensures that dyes, especially the yellow ones, are easy to perform and with which photographic layers 25 have excellent lightfastnesses without also which are well suited to discoloration of the image after prolonged exposure for the silver dye bleaching process. white entrances.

It has now been found that azo dyes The production of the colored gelatin can high fastness properties and good brilliance in general before the preparation of the photographic emulsion Formula 30, but the colored gelatine can also be used

be added as blend gelatine to an already fully ripened (X) _n photographic emulsion.

The use of the dye gelatins produced according to the invention is not limited to 35 image layers for the silver dye bleaching process, where they are preferably used, but they can also be used as filter layers and for. Clipping filters for general color photographic purposes or for where F represents a dye residue and X = H, photocrosslinkable gelatin layers by sensiti-alkyl, preferably up to 18 carbon atoms, alkoxy, halogenation with bichromate or suitable azides or logen, such as chlorine or bromine and η - 1 azide derivatives are used until 3 is reactive with very good fixation yields
Let gelatine set and become absolutely diffusion-proof. The small percentage of not
The converted dye can easily be washed 45
and be completely removed. The dye

/ -Cl

The preparation of the reactive dyes according to the invention used in the following examples is explained using the following example:

For the solution of 48.7 parts of the aminoazo dye of the formula

can be connected to the reactive residue directly by means of a chemical bond or via bridges be bound. Such intermediate links are described in Belgian patent 613,586. Groupings of the general formulas have proven particularly suitable for this

H, N

N-SO ₂ -R

HO ₃ S

- N - CO
R.

(obtained by coupling diazotized 4-nitroaniline-2-sulfonic acid with 1- (2'-chloro-5'-sulfophenyl) -3-methyl-5-aminopyrazole and reduction with Na? S) in 1400 parts of water are added 5 parts feiogepulvertes2,3-dichloroquinoxaline-6-carboxylic acid chloride and the mixture is stirred at about 45 ⁰ C for 4 hours

proven. R denotes hydrogen or a 65 with ongoing blunting of the salt-alkyl radical formed, preferably a lower residue with up to acidic to pH 4 to 6, up to by diazotia ^ en one to 3 carbon atoms, such as methyl or ethyl. Preferably sample and coupling with 1-Hydroxynaphthalnals Bridge members are carbonamide groups. 4-sulfonic acid no more free amino group after-

is demonstrable. The reactive dye formed of the formula

CO-HN

Cl

HO, S

is precipitated by adding 150 parts of sodium chloride, filtered off and dried at 50 ° C in a vacuum.

The dye used in Example 9 was according to the information in Belgian Patent 613 586, Example 30 received.

example 1
5 g of the yellow dye of the formula

SO ₃ Na

Cl

are dissolved in 100 ml of water and mixed with 200 g of a 20% gelatin solution at 50 ° C. Then one adds immediately enough 2N sodium hydroxide solution with stirring that one has a pH value of 11.0 to 11.5 is obtained by holding the solution for 30 minutes. The pH value is increased by adding 1N HCl then reset to 6.5, the gelatin poured thinly on a glass plate and cooled. After this When gelling, the gelatine is detached and soaked in running water at 20 ° C for 6 hours, whereby, in addition to the salts resulting from the neutralization, also the small proportions of hydrolyzed or unreacted dye can be removed. The reactively colored gelatin is melted at 40 ° C and 500 ml of a likewise melted, highly sensitive silver bromide emulsion added, which was produced in a known manner and the usual casting additives, such as Plasticizers, stabilizers, wetting agents and hardening agents. Then you shed on a baryta paper backing with a layer thickness that allows a silver application of 0.5 to 0.7 g / sqm is equivalent to. After drying, a sample is exposed to white behind a stepped gray wedge Light and processed as follows:

1. 5 minutes black and white development in a developer with the following composition:

1 g of p-methylaminophenol
13 g sodium sulfite, sicc.
3 g hydroquinone
26 g of soda

1 g potassium bromide in
1000 ml of water

2. 1 minute soak

3. 5 minutes of fixation

200 g sodium thiosulphate, crystall. 20 g potassium metabisulphite, sicc. in 1000 ml of water

4. 5 minute soak

5. 5 minutes hardening (formalin 4%)

6. 5 minute soak

7. 15 minutes of color bleaching

10 g potassium iodide
10 g sodium hypophosphite 80 ml quinoline

75 ml of sulfuric acid, concentrated in 1000 ml of water

8. 5 minute soak era Tetrasodium ethylenediamine tetraacetate 9. 5 minutes bleach-fix era Soda, sicc. 26th G Iron (III) chloride, crystall. 24 G Sodium sulfite, sicc. 15th what ' Sodium thiosulfate in 13th ml water 200 800

10. 20 minute final soak

After drying, you get a well-bleached yellow wedge with neat gradations, the shows no dye diffusion and has excellent lightfastness.

With suitable hardening of the starting material, the first fixation and the additional hardening can be carried out can be omitted without affecting the photographic result.

Example 2

Make a colored gelatin in the same amount as indicated in Example 1, add a solution of 20 g of gelatin in 250 ml of water after washing and melting and make in a known manner by adding 200 ml of a 10% silver nitrate solution and subsequent precipitation of the silver halide at 60 ⁰ C with 150 mL of 10 ° / pigen potassium bromide which are about 4 ° / o of potassium iodide, which contains a photographic emulsion produces the approximately 15 g of silver per liter. After digestion for 20 minutes at 70 ^° C., the mixture is gelled by cooling, the emulsion is divided into fine strips and freed from soluble salts

CO -NH

Watering. After renewed melting at 4O ⁰ C are employed an additional 20 g of gelatin to and keeps the emulsion up to maturation at 60 ⁰ C. After adding the usual coating additives is cast, exposed and processed as described in Example. 1 A similar color wedge is obtained as before.

Example 3

Results similar to those in Examples 1 and 2 are obtained if those described there are adhered to Processing instructions by mixing in equal quantities the following colorants with gelatin implements:

SO ₃ Na

CO-NH

SO, well

Cl

SO, H

10

CO - NH J - SO ₃ H

CO-NH

Instead of thiourea 30 to 50 g in its composition in Example 1, concentrated hydrochloric acid 60 The specified bleach bath can also contain a thiourine up to 120 ml, 2-hydroxy-3-aminophenazine 2 to 5 mg. Fabric bleaching bath of the following composition with the same. Brilliant yellow dye goods are also achieved here Success can be used: KBr 40 to 60 g, 35 images of high authenticity with good whiteness.

Example 5 g of the purple dye of the formula are dissolved

HO NH - CO

N =

NaO ₃ S

SO ₃ Na

SO, well

in 100 ml of water and fixes the dye reactively on the gelatin, as described in Example 1. When preparing the casting solution, it is additionally sensitized with 15 mg of a merocyanine, as in FIG British Patent 1,078,227, Example 2, and wearing the colored emulsion obtained in a thin layer on a base of white pigmented cellulose acetate, so that a silver application of 0.6 g / sqm is created. After drying, a sample of this material is exposed from behind strict yellow filter to eliminate and process the intrinsic sensitivity of the bromide silver emulsion, as described in example 1. A purple color wedge with clean gradations and is obtained completely uniform color surfaces with good lightfastness.

In the same way as indicated, the process according to the invention can also be used for production of three-layer material, with one or all three image dye layers being reactively pinned May contain dyes.

Claims (4)

Patent claims: 1. A process for making azo dyes resistant to diffusion in photographic gelatin layers by reacting these azo dyes with gelatin, characterized in that dyes of the following general formula
60 65 where F is an azo dye radical and X = H, alkyl, alkoxy or halogen and 809 537/531 η = 1 to 3 means to be reacted with gelatin in an aqueous solution which has a pH of 10 to 13 at a temperature of 45 to 50 ° C. 2. The method according to claim 1, characterized in that such dichloroquinoxaline azo dye compounds can be used for the reaction in which the azo dye grouping via bridges of the following general formulas associated with the dichloroquinoxaline residue: - N - SO ₂ - or - N - CO - where R is hydrogen or an alkyl radical. 3. The method according to claim 2, characterized in that azo dyes are used, whose alkyl radical is methyl or ethyl. 4. The method according to claim 3, characterized in that azo dyes are used, whose azo dye residue is connected to the dichloroquinoxaline residue via a carbonamide bridge is. 809 537/531 3.611 © Bundesdruckerei Berlin