SU212748A1 - METHOD OF MANUFACTURING HALOGEN-SECONDARY PHOTOGRAPHIC EMULSIONS - Google Patents

Description

The invention relates to a process for the manufacture of halide-silver photographic emulsions using, as stabilizers, as well as stabilizers, with a sensitizing effect, triazole derivatives. A known method for the manufacture of halide-silver photographic emulsions is that the halide-silver emulsion is grown, melted and subjected to chemical maturation, at the end of which stabilizers are introduced into the emulsion. It was found that as stabilizers and stabilizers of optical sensitizers with good devoulling effect, compounds of the general structure I-VI N-NH / VY || 1IjI jJJf; H CH-CH (Zj kjk CH-CE (z; Y is S or NRv; Z is a quinoline residue or benzthiazole; Zj is a residue of a ketomethylene compound; RI, Ra, Rs, Re is alkyl; R4, Ra is hydrogen, alkyl, carboxyl, droxyl, cyan, acetobenzoyl, or OONH4 is a group ; Ry is alkyl or aryl; X is an acid residue. Example 1. Chlorosilver photographic emulsion is synthesized as follows: Prepare two solutions of recipe: Solution 1

Solution 2

41 ° C Silver nitrate 37.5 g Water 500 ml

Within 1 minute, solution 2 is poured into solution 1. After 20 minutes of stirring, mix the students. The jelly is ground and crushed to a conductivity of 1.4-1,. The resulting emulsion is melted and subjected to chemical ripening at 52 ° C. At the time of maximum photosensitivity, when stabilized in the form of alcoholic or aqueous solutions, stabilizing substances are introduced. Their concentration in the emulsion is 4-mol / mol Ag.

Immediately after the introduction of stabilizing substances, the first plates (3 ml of the emulsion are poured onto a 9 x 12 cm plate), the second - after 2 hours of chemical maturation. The stabilizing effect is assessed by the change in photovalence: photosensitivity, determined by criterion 0.2 over the density of the veil (S 0.2 + Do), veil and contrast (Do and y) of the stabilized emulsion compared to the unstabilized for the specified period of maturation.

In tab. 1 shows some of the substances proposed as stabilizers and stabilizers-optical sensitizers, and their properties in comparison with the known stabilizers.

From tab. 1 shows that the stabilizing and deviating properties of the proposed substances are either identical with the properties of the known stabilizers (s, or exceed them. For example, the ammonium salt - (11,21-dimethylbenzimidazolyl-b1) -5-methyltriazolyl - 4-carboxylic acid devualizes the emulsion so the same as 5-methyl-7-hydroxy-1,3,4-triazindolicin, it stabilizes better and does not suppress photosensitivity at all. The stabilizing effect of some of the applied substances is accompanied by an increase in photosensitivity (see Table 1).

Example 2. Highly sensitive ammonia sensitized with rhodanum gold bromine-silver-emulsion emulsion is subjected to chemical maturation at 52 ° C to maximum photosensitivity. Portions of such an emulsion are stabilized with various stabilizers, after which they mature for another 2 hours at the same temperature. During this process, plates are poured (5 ml of the emulsion on a 9X12 slit plate), which, after drying and exposure on an FSR-4 sensitometer, are developed in the Chibisov developer for 8 minutes at 20 ° C. As in example 1, the concentration of stabilizing substances in the emulsion is 4-mol / mol Ag.

In tab. 2 shows the results of these tests, which indicate that when applied to a highly sensitive emulsion, 2-methyltriazolo- (4,5-d) -benzthiazole and 2-methyltriazolo- (4,5-e) -benzthiazole occupy a middle position between the stabilizers 1 -phenyl-5-mercaptoterazole and 5-methyl-7-oxy1, 3,4-triazaindolicin for stabilizing, depressant and anti-antiviral capacity.

Example 3. A chloro-silver photographic emulsion, the synthesis of which is described in Example 1, is subjected to chemical maturation at 45 ° C for 45 minutes. To the portions of this emulsion, stabilizer-optical sensitizers are added in an optimum concentration for optical sensitization. The test results of plates watered with sensitized emulsions are given in Table. 3

From tab. 3, it can be seen that using the proposed optical stabilizers, the photosensitivity of the chloro-silver emulsion can be increased by a factor of 10–20 while simultaneously reducing the veil. 1-Methyl 3, 3-diethyl-6- (3-ethyl-4 -carboxy-5-methyltriazolyl-1 (imidatiacarbocyanine perchlorate and 3-ethyl-5- 3-ethyl-6- (4 -carboxy-5methyltriazolyl-1) - Benzthiazolinylidene-2ethylidene-thiozolidin-2-one-4 (Tables 1, 3) are more effective than the known stabilizer-sensitizer 2-amino-4-methylthiazolyl-5-azobenzene, although the long-wavelength sensitization limit for these substances lies 60 mmk further.

. Example 4. General procedure for the synthesis of triazoles. To 0.01 mol of sodium ethoxide in 40 ml of absolute alcohol, 0.005 mol of the corresponding starting azide, 0.02 mol of acetoacetic ester (or acetylacetone, or malonic ester, or cyano acetic ester, etc.) are added and heated on a water bath for 2 -3 hours The reaction mixture is then left for 24 hours at room temperature. The precipitate is filtered and purified. For example, the condensation product of 1,2-dimethyl-6-azidobenzimidazole with acetoacetic ester is precipitated from an ammonium solution with acetic acid, and then crystallized from methanol.

Ammonium salts of triazolecarboxylic acids are obtained by passing ammonia gas through a hot solution of a triazolecarboxylic acid in absolute alcohol. The resulting ammonium salts precipitate.

Example 5. Getting Quaternary salts of 1,2,3-triazoles. These suns are obtained by heating 0.005 mol of the starting 1,2,3-triazole with 0.02 mol of alkyl halide in a sealed ampoule at 140 ° C for 5 hours. Quaternary salts are washed from resinous products with boiling acetone. To facilitate purification, the resulting iodides are converted to perchlorates. For this, 1 of methyl or ethyl iodide is dissolved in ethanol and an alcoholic solution of 0.6 g of sodium perchlorate is added. The precipitate is filtered and crystallized from alcohol.

Table 1

azole. These compounds are obtained by heating the corresponding quaternary salts of 1,2,3-triazoles with orthoformate in nitrobenzene for 1 hour at 150-160 ° C. From the cooled solution, the dye is precipitated with ether, washed first with it, then with a small amount of water, methyl alcohol and again with ether. Further purification was dried; it was recrystallized from alcohol. Symmetric trimethine cyanines benzthiazole get similar. However, acetic anhydride is used as a solvent, in which the reaction takes place over 30 minutes at 120 ° C. The precipitate is filtered, washed with alcohol and ether. For cleaning, the dye is converted into perchlorate, for which a warm aqueous solution of sodium perchlorate is added to a hot water / alcohol solution. With

table 2

cooling, the dye appears as perchlorate.

Asymmetric trimethinecyanines are obtained by heating for 30 minutes equimolar amounts of the corresponding quaternary salts of 1,2,3-triazoles with 2-acetanilidinylbenzthiazole iodomethyl in acetic anhydride in the presence of trimethylamine. The dye formed is precipitated with ether.

or it falls out when it is cool. The benzimidazole dyes are purified by recrystallization from alcohol. For the same purpose, benzthiazole dyes are converted into perchlorates, they are dissolved in aqueous alcohol, the solution is heated and

a warm solution of sodium perchlorate is added to it. Dye perchlorates precipitate upon cooling,

Table 3