DE2145391A1 - Colouring gelatine with dyestuffs - having reactive alpha-beta dibromopropionyl or alpha-bromacrylyl gps for colour bleach process - Google Patents

Abstract

Coloured gelatin, is produced by reacting gelatin with water-sol. reactive dyestuffs contg. at least one reactive alpha, beta-dibromopropionyl and/or alpha-bromacrylyl gp. bound to dyestuff mol. through -CO- gp. and pref. to N atom or esp. -NH- gp of dyestuff mol. Technique is useful for prodn of permanent filters, colour coats for 3-colour photography and (Ag) colour bleach process.

Description

Process for making colored gelatin.

The invention relates to a process for the production of colored Gelatin, and the process is characterized in that one uses the gelatin converts water-soluble reactive dyes, as reactive groups at least a residue of α, β-dibromopropionic acid bound to the dye molecule by the -CO group and / or a-bromoacrylic acid.

These acid residues, which correspond to the formula -OC-CHBr-CH2Br or -OC-CBr = CH0, can preferably be via a nitrogen atom, in particular via -NH- or like how Groups to be bound to the further dye molecule. This latter part of the molecule, which contains the chromophoric and auxochromic groups, can be modified depending on the intended use of the gelatin.

For example, such dyes are used for the silver dye bleaching process used, which by image-wise generated silver depending on its amount present, are bleached, for example azo or azoxy dyes or phthalocyanines.

A number of reactive dyes of the above composition are known and, moreover, these dyes can be used according to customary, known per se Methods are made.

They are expediently mixed with gelatin in an aqueous medium, e.g. at Temperatures from 10 to 600 ° C. and optionally in the presence of an acid-binding agent Means, implemented For example, 5 to 20% of the time aqueous gelatin solution, the necessary amount of reactive dye, if necessary in the form an aqueous solution, and let the whole stand for a while.

In some cases the reactivity of the dye is so great that that the implementation is practically complete without further ado. Also can the gelatine absorbs larger amounts of the released hydrogen halide, without the pH value dropping too much.

It can also be beneficial by adding acid-binding agents Agents such as sodium bicarbonate, sodium carbonate, sodium phosphate, sodium acetate, Sodium borate, sodium hydroxide, or the corresponding potassium compounds, the implementation to promote and accelerate.

When the reaction has ended, the colored material is expediently optionally in the molten state, for example at 40 to 600 ° C., with an acid such as hydrochloric acid, acetic acid or citric acid, added so that the pH value e.g.

goes back to 5.6 to 5.8, whereupon the gelatin solidifies again leaves.

The gelatine can now be crushed, e.g. made into noodle form, and by methods known per se by soaking unbound dye and Salts are exempt.

Very high color yields can be obtained, what from it evident is that the wash water will soon run off colorless, a sign that only a little The dye has not reacted with the gelatin. Optionally, the result can nor by adding suitable aids, such as .3. Implementation products are more highly modular aliphatic amines with ethylene oxide.

The colored gelatins obtained by the present process can e.g. for the production of durable filters, but especially for layers of paint three-color photography.

One can be applied to a suitable carrier with the reactive dyes Sensitize converted gelatine with alkali chromates or alkali dichromates, for example and then expose, the gelatin being hardened under the influence of light, so that After removing the unhardened gelatine in a warm water bath, a tanning pattern emerges can be achieved.

The gelatins reacted with reactive dyes can also be mixed with Silver halide emulsions are mixed, or there can be silver halide in the colored gelatin can be produced directly. After exposure, a silver image can be produced to be developed. By tanning silver bleaching one arrives at a tanning picture, which can be washed out. It is used for the reaction with the gelatin in an image-wise manner bleachable dyes, such gelatin can also be used for a Color bleaching process, especially for the silver dye bleaching process.

The color gelatins reacted with reactive dyes can also be used also use in the production of mixed grain emulsions. The colored gelatin layers can also be in the neighborhood, e.g. I3. in direct contact with a light-sensitive, e.g.

layer containing silver halide.

In the examples below mean where nothing else is noted is, the parts are parts by weight and the percentages are percentages by weight.

Example 1 1 g of the reactive dye of the formula are dissolved in 5 com water cold, and the solution is added to a 400 C warm gelatin solution of 20 g gelatin in 200 com water. By adding about 15 .mu.m of a 4% sodium hydroxide solution, the original pH value is brought from 5.6 to 10> 5 under control. Now the mixture is left to its own devices for 12 to 24 hours at room temperature. The goods are then melted at 40 to 4 ° C. and a pH of 5.6 to 5.8 is set by adding about 7.5 to 10% acetic acid. The mass is allowed to solidify in the refrigerator and the jelly is cut into fine pieces, which are now freed from the salts and the unfixed dye in running cold water until the wash water runs off practically colorless.

A lively bluish-red colored plate is obtained which is as follows can be used: The optical density is determined by casting a test on a glass plate of the red colored gelatin determined. After that, this is covered with colorless gelatin adjusted to a certain density and optionally with silver halide emulsions mixed.

The gelatin can also be dried and then swelled again placed in water, normal on.

With the reactive dyes of the formulas or yellow-colored gelatins are obtained which, as described above, can be used for tan bleaching images or the silver dye bleaching process, in the latter case also, for example, in three-layer material.

In addition, instead of using the dye of the formula (1), gelatin can be colored with the dyes of the formulas below in the manner indicated, where X can be an H2C = BrC-CO group or a BrH2C-BrHC-CO group.

- yellow - - bluish red - - bluish red - - red - red - red - - orange - - green - - blue - Example 2 The reactive dye used here is one of the following dyes a) dye of the formula (1) - red - b) dye of the formula - yellow -c) dye of the formula - red -d) In 3-, 3'-, 3 ## and 3 "'positions further substituted copper phthalocyanine, with an average of 2.5 H03S groups and 1.5 blue - present 1 to 2 g of dye are mixed in 50 com of water, then anhydrous sodium acetate is added and the resulting solution is added to a gelatin solution of 20 g of gelatin in 200 com of water. It is kept in a water bath for 2 to 6 hours at 35 to 400 ° C. The gelatine is then solidified and cut into noodle form and then washed out with cold water for several hours.

They can be used to produce colored layers for photographic applications Use purposes as described in Example 1 above.

Example 3 0.25 part of the reactive dye of the formula are stirred in 25 parts of cold water, and the solution is added to a gelatin melted at 400 C, which contains 10 parts of gelatin in 100 parts of water. The mixture is adjusted to pH 10 with sodium hydroxide and then left to itself at 18 to 200 C for 24 to 48 hours or held at 30 to 350 C for 12 hours. The cooled, solidified gelatin is made into noodle form and washed with cold water to remove the unfixed dye. It is colored blue-red and can be used for the construction of photographic color material.

Example 4 0.3 part of the blue dye of the formula is dissolved in 30 parts of water, add the solution to 100 parts of an aqueous gelatin solution containing 10 parts of gelatin at 400.degree.

The pH is adjusted to 10 and the gelatin solution is poured onto a glass plate, for example 10 cm3 on an area of 13 cm. 18 cm. After the gelatin has dried and after storage for 24 hours, the non-bound dye can be dissolved out of the gelatin with water. After repeated drying, a blue gelatin layer is obtained on the glass. It can be converted into a gelatin tanning pattern and wash-out relief in a known manner, for example by sensitizing with ammonium dichromate, copying and developing with water contains in 1000 parts of a 6 to 7% gene gelatin. To this are added 10 parts of a dye solution containing 1.2 parts of the dye of the formula contains dissolved in water. If desired, 10 parts of a 1 to 4% solution of a wetting agent or dispersing agent such as saponin are also added.

10 g of such a mixture are placed on a 13 cm glass plate. 18 cm potted and dried. After a few days of storage at elevated temperature and humidity, most of the dye is chemically bound to the gelatin. The layer can be used in the silver color bleaching process and as a partial image of a three color material. A yellow partial image is obtained. The small portion of the dye that is not bound to the gelatin can easily be washed out in the course of the development process. Instead of the dye of the formula (10) it is also possible to use the dyes of the formulas which all give yellow colored gelatins can be used.

EXAMPLE 6 0.25 to 0.3 parts of dye of the formula are added at 350.degree. C. to 100 parts of a 10% strength aqueous gelatin dissolved in 25 parts of water. The pH is adjusted to 8.5 and the mass is allowed to react for 48 hours at 180 ° C. or 6 hours at 350 ° C. The colored gelatin is solidified, finely divided, washed to remove the non-bound dye and for further processing with fresh , uncolored gelatin brought to the desired color density. This red colored gelatin can be used to build up the purple layer in the three-layer material.

Example 7 0> 1 g of the dyes mentioned in the table below are dissolved in 5 ml of distilled water, add the solution at 300 ° C. to a solution of 2 g Gelatin in 18.5 ml of water. The pH is then adjusted to 10.0 with 0.5 N sodium hydroxide solution and the solution was brought to a volume of 27.5 ml with water. After 18 hours Standing at 300 ° C., 10 ml of it are placed at 400 ° C. on a 13 cm ~ glass plate Poured 18 cm and allowed to solidify for 10 minutes. A sample is made immediately dried and another immediately after solidification under running tap water soaked at 200 C for 2 hours and then also dried.

The dried samples (non-watered and watered) are measured at 12 points with the appropriate filter using a conventional densitometer (Gretag D 33) and the mean filter density is calculated from the 12 filter density values. The difference between the filter densities before and after the soaking, resulting from the mean values, is calculated and expressed in percent density loss. The stated value corresponds to the unfixed dye, the difference to 100% corresponds to the proportion of the fixed dye. Dye loss of density of fixed dye in% in% (4) 9 91 (2) 11 89 (8) 15 85 (11) 9 91 Example 8 The procedure described in Example 7 is repeated and the dye of the formula is used and if the reaction solution is left at pH 10 for two hours, the following results are obtained: Loss of density he fixes dye in% in% 200 C 12 88 300 C 11 89 400 C 10 90

Claims (5)

Process for the production of colored gelatin, in particular for the silver dye bleaching process, marked by the fact that gelatin is used with converts water-soluble reactive dyes, the reactive groups at least one residue of α, -dibromopropionic acid bound to the dye molecule by the -CO group and / or the a-bromoacrylic acid. 2. The method according to claim 1, characterized in that one gelatin reacts with such dyes, their aß-dibromopropionic acid residues and / or a-bromoacrylic acid residues are bound to the rest of the dye molecule via a nitrogen atom. 3. The method according to claim 2, characterized in that one gelatin reacts with those dyes whose a, ß-dibromopropionic acid residues and / or a-bromoacrylic acid residues are bound to the rest of the dye molecule via an -NH group. 4. The method according to any one of claims 1 to 3, characterized in that that one reacts gelatin with azo dyes that contain at least one atom group of the formulas -OC-CHBr-CH2Br and / or -OC-CBr = CH2. 5. Method according to one of Claims 1 to 4, characterized in that that the gelatin in an aqueous medium at temperatures between 10 and 600 C, if appropriate in the presence of an acid-binding agent, with the reactive dyes implements.