SU1038919A1 - Method of producing ultra fine grain high-resolution bromine-iodine silver photographic emulsion - Google Patents

Description

11 The iso-grams are related to methods for producing halogen-hygroscopic photographic emulsions and can be used in the chemical-photographic industry in the manufacture of very fine-grained photographic materials used, for example, as photo masks. A known method of manufacturing a particularly fine-grained bromide-silver photographic emulsion by means of emulsification, physical and chemical maturation and preparation for irrigation. Moreover, at the stage of preparation for irrigation, compounds are introduced into the emulsion, which make it possible to increase the stability of the latent image (5,5-diethyl-2,2-dimethyl-thiazolidine carboxylic acid) 1. However, the emulsions obtained by this method have unsatisfactory photosensitivity, resolution, sharpness of the edge and stability of the latent image. The closest to the present invention is a method of producing a special fine-grained, high-resolution bromine iodide-silver photographic emulsion using a chemical sensitizer by emulsification, physical ripening, a student, a sample, a sample, an emulsification, a chemical sensitizer by emulsification, physical ripening, a student, a sample, a sample, a prod- , freezing, chemical ripening and preparation for irrigation, according to which The chemical sensitizer uses sodium thiosulfate, which is introduced during the chemical maturation stage in the amount of 0.25 g per 1 kg of cepe6paC2.3f. However, the emulsions obtained by the known chow have unsatisfactorily low photosensitivity (0.02 units of GOST), resolution (up to 1730 LIN. / Mm)., Sharpness of the edge (up to 0.6 µm) and stability of the latent image during storage, (50% at, 0 for 8 h). , The purpose of the invention is to increase the sensitivity, resolution, sharpness of the edge and the storage time of the latent image. The goal is achieved by the fact that according to the method of making special fine-grained high-resolution bromo-silver-photographic emulsions using a chemical sensitizer by emulsification, physical maturation, freezing, chemical aging 19 and maturation, preparing for irrigation, as a chemical sensitizer, the compound used is a compound, a medium, and a mixture of organic sensitization. or (i). where (i); C (I I); or 1; xy - CH2-CH - or which is introduced into the emulsion in an amount of 0.01-5.0 g per 1 kg of silver at the stage of emulsification or physical ripening, or chemical ripening, or preparation for irrigation. The introduction of compounds of the general formula (1) or (m) in the manufacture of a very fine-grained high-resolution bromide-silver-photographic emulsion at the stage of emulsification or physical maturation; or chemical ripening allows increasing the photosensitivity, resolution, edge sharpness and storage time of the latent image and does not cause adverse effects on other properties. Example 1. Obtaining compounds of structural formula (M), where (|),, x-ys-CH-CH, -. V In a boiling mixture consisting of 900 ml of ethyl alcohol, 900 ml of water. 6 g of anhydrous sodium carbonate, 100 ml of ethyl alcohol containing 10.0 g of bis- (2-chloroethoxy) -ethane and IIO. 1,2 g of bis- (p-mercaptoethoxy) ethane are added dropwise over 1 hour. . The mixture is left overnight under reflux, cooled, filtered and evaporated. A precipitate of 9.0 g, a brownish paste, is transferred to a Lorist clay plate and 0.16 g of white fibrous crystals are obtained with a mp. 91 ° C, m.v., 296. 2.96 g of the compound 7,13,1b-tetraoxy-1,10-dithiacyclooctadecane thus obtained is dissolved in 100 ml of ethyl alcohol VI; 0.17 g of silver nitrate is introduced (ratio 1 : 1 mol) to obtain a 3.0% alcoholic solution .13,1b-tetraoxy-1,10-dithiacyclo-octane - Ad (I). To isolate the compound into solid form, the solution is cooled by placing in a refrigerating chamber (-5 ° C) for slow evaporation of the solvent. Vypavshi white transparent crystals are purified by fractional crystallization. M.p. 1611bz®s. The fact of complexation is established by NMR spectroscopy. NMR spectra were recorded on a JEOL high resolution C-60HL spectrometer. The group of signals corresponding to the isotopes of the polyester ring located near sulfur, when silver ions are added to the solution (heavy solvent), is shifted towards the weaker floor. Chemical shift 0.23. Example 2. Getting Connected. structural solution (I), where To a solution containing 6.6 g of bis- (2-br6-methyl) -rffir in 1300 ml of ethyl alcohol, was added dropwise over 2 hours under reflux a solution of carbonate monohydrate sodium in the amount of 24.8 g dissolved in 8 l of 50% ethanol solution. The mixture is then boiled for 72 hours under reflux, after which most of the solvent is removed in vacuo to a volume of 500 ml. After some time after settling, the cloudy residue exfoliates and the heavy oily layer is separated. The aqueous layer was extracted with four portions of ethyl acetate with a total volume of 200 ml. All this, together with the oil, is dried with anhydrous sodium sulfate, the solvent is removed by evaporation in vacuo, and 16.0 g of a colorless oil are obtained with m, boiling 133–1.2 ° C at 0.17 mm. There is some solidification in the apparatus during the distillation process and the pure product slowly partially crystallizes at room temperature. M.p., 22 ,, m.v., 208, 2; 08 g of compound i thus obtained, 10-DYOXY-1,7-dithiacyclo-octane is dissolved in 100 ml of ethyl alcohol to obtain an alcoholic solution. 3. Preparation of the compound of structural formula (It), where xy (o),. 100 ml of ethyl alcohol containing 14.0 g of 1, 2-bis are added dropwise to the boiling mixture consisting of 900 ml of ethyl alcohol, 900 ml of water 6, k g of anhydrous sodium carbonate. (p-chloroethoxy) benzine and 11.0 g of 1,2-bis- (p-mercapto-ethoxy) 5 tane. The mixture is left overnight with a reflux condenser, cooled, X1T filtered and evaporated. Sediment 9, g, gum paste, is transferred onto a porous clay plate and 0.16 g of white fibrous crystals are obtained with m, pl. 91 ° C, m.v., G, g, the compound 2,3-benzo-1,4,10,13-tetraoxy-7,1b-dithiacyclooctadeca-2-ene thus obtained is dissolved in 100 ml of ethanol to obtain 3, alcohol solution. Example k. The preparation of the compound of structural formula (I), where (1I),. 0.19 g of copper nitrate (1: 1 mol) ratio, 2, 4,10-dioxy alcohol solution, are introduced into 100 ml of a 2% alcoholic solution of 4,10-DIOXI-1.7 dithiacyclooctane obtained analogously to example 2. -1, 7-dithiacyclo-octane-Cu (II), Identification is carried out analogously to Example 1, Example 5: Preparation of the compound of structural formula (D), where (1),. In 100 ml of a 2% alcoholic solution of 4,10-DIOXI-1.7 dithiacyclooctane, prepared analogously to example 2, 0.17 g of silver nitrate (ratio 1: 1 mol) was obtained to give 2, an alcoholic solution 4.10- Dioxy-1, 7 dithiacyclooctane - Hell (|). The identification is carried out analogously to example 1. PRI K 6, Preparation of the compound, the scientific research institute of the structural formula (II), where (| t), xy -CH9-CH2.-, K 2.96 g4 , 7,13,1b-tetraoxy-1,10-dithiacyclo-octadene, prepared as in example 1, dissolved in 100 ml of ethyl alcohol, was added 0.19 g of copper nitrate (1: 1 mol ratio, to give a solution of 4,7,13, Tbtetraoxy-, 10-dithiacycloooctadecane-C (1 O. Identification is carried out analogously to example 1. Example 7 (prototype), High-resolution prototype emulsion is synthesized in prototype, B apparatus of 270 liters, equipped with high-speed propelle Rny agitator - with a speed up to 2000 rpm

and jacketed, demineralized water in an amount of 675 ml, 67.5 g of inert gelatin and 0.3 g of potassium bromide are loaded, then solutions a and b are prepared.

Solution a contains ml of desalinated water and 0.5 ml of silver nitrate.,

Solution b will contain a ml of desalinated water, 28.5 g of potassium bromide, 1.6 g of potassium iodide and 13.5 ml of an aqueous solution of ammonia with a density of 0.986 l / 25% pacTBOfj). The emulsification is carried out instantaneously within 1-2 seconds. Compressed nitrogen is simultaneously dosed into the apparatus and into the apparatus with a rotating mixer with a speed of 2000 rpm. After carrying out physical ripening, while stirring the reaction mass, solution c is introduced into the apparatus for 10 seconds.

The solution contains i ml of desalinated water and 2 g of citric acid. Then, the resulting emulsion is cooled to 35 ° C, and the freezing is carried out in a cuvette, cut into worms and washed with demineralized water for 1.5-2 hours to an electrical conductivity of 3000-L cm and a silver electrode potential of mV. After that, the emulsion placed in a cuvette is subjected to freezing at -20 ° C. For a day and washed to remove ice with cold water.

Chemical ripening of the resulting emulsion is carried out as follows.

The emulsion is loaded into the melter. At a temperature of 60 ° C and stirring at a speed of 200 rpm, 7 ml of a 0.1% aqueous solution of sodium thiosulfate (0.25 g per 1 silver) are introduced into it. Chemical ripening is carried out for 0 min, then the emulsion is cooled to. Before watering, the following additives are successively introduced into the emulsion: 12 ml of 0, alcoholic sensitizer solution 3712 with the chemical name 1- | -oxyethyl-3-H-propyl-5 (3-gcarboxyethylbenzoxazolinylidene-2 ethylidene) -imidazolidinethion- (2) -CH C) and empirical formula C Hfe jOgN-jS; 2 ml of a 0.5% solution of a stabilizer 1-phenyl-5 mercdptotetrazol (sta-7), 8 ml of an alcohol solution of a tanning agent with the chemical name bis-ethylene imidipipic acid; you.and 8 ml of 0.5% alcohol plant.

Thief tanner DU-801 with the chemical name 1,3,5-tris- (acryloyl) -1,3, 5-triazine. Then the photographic emulsion is incubated for 0.5 to 1 h and filtered. Thereafter

watering the emulsion with a THICKNESS

6 µm onto glass plates with anti-aurale and adhesive layers.

Photographic processing of materials was carried out at a temperature of 20 ± 0.5 ° C in a metolhydroquin developer for 5 minutes, diluted 3 times with the following composition:. 50% solution

potassium bisulfite 600 ml Water 110 ml

Metol 7.5 g

Hydroquinone25.0 g

Metaborate YO potassium g Sodium hydroxide 20 g Potassium bromide 20 g Vodado 1000 ml

and fixing solution composition: Thiosulfate

rub 250 g

Metabisulphite

kali 30 g

Wadado 1000 f-sh

Photosensitivity is monitored by the results of sensitometric tests on an FSR- and RDA-6 densitometer Sakura. The sharpness of the image edge and resolution is determined by the projection method using a RP-2M resolvometer followed by visual assessment on a MOB-i-t5 microscope according to GOST. In addition, the edge sharpness is judged by the results of blurring (: an image of a chrome standard followed by microscopic image control at 600x magnification and expressed in absolute units.

The constancy of the dispersion of the emulsion before and after the introduction of additives is monitored using an electron microscope. The regression of the latent photographic image is evaluated by the change in the resulting optical density after processing depending on the storage time of the exposed material. The data obtained are shown in the table.

Example 8 (control). The preparation and testing of a photographic emulsion is carried out similarly with Size 7, but only at the stage of preparation for irrigation after the introduction of tanning agents. Into the emulsion enter tT, O ml of 1% aqueous solution of 5.5-Diethyl-2,2-dimethyl-thiazolidine carboxylic acid . The data obtained are shown in the table.

Example 9. The preparation and testing of photographic emulsions was carried out analogously to Example 7 with the difference that, at the emulsification stage, solution b contains the formula of general formula (I), where p-O, in an amount of 5 g per 1 kg of silver, which is 7 ml 2% alcohol solution, 10-dioxy-1,7-dithiacyclooctane. The data obtained are shown in the table. Example 10. Preparation and testing of a photographic emulsion is carried out analogously to example 7 with the difference that at the emulsification stage solution b contains a compound of the formula (11), where (|), .-, at the rate of 0.01 g per 1 kg of silver, which is 0.3 ml of a 0.1% alcohol solution A, 7.13, Tb-tetroxy-1, 10-dithium Cycloooctane Ad (|). The data obtained are shown in the table. EXAMPLE 11 The preparation and testing of a photographic emulsion is carried out analogously to Example 7, only on. the chemical maturation stage, before introducing sodium thiosulfate into the emulsion, inject a compound of the general formula (II), where xy (£ 3C per 2 kg per 1 kg of silver, which is 1.5 ml of 3.3% alcoholic solution 2 , 3-benzo-1, 10,13-tetraoxy-7, 1b-dithiacyclo-octadeca-2-ene. The data obtained are shown in Table 1. EXAMPLE 12 Production and testing of a photographic emulsion is carried out analogously to Example 7, only at the stage of chemical ripening, before introducing sodium thiosulfate into the emulsion, a compound of the general formula (|), where (11),, at the rate of 5 g per 1 kg s ribs, that is, 0 ml 2.2% alcoholic solution

, 10-dirxy-1,7-Diethylcycloctane (11). The data obtained is given in the table.

EXAMPLE 13 The preparation and testing of a photographic emulsion is carried out analogously to example 7, only at the stage of preparing the emulsion according to / 1ive after the introduction of tanning agents is the compound of general formula (I) introduced into it;

j de x «Aq (l), l-1. in the amount of 0.01 g per I kg of beber. which is 1 ml of 0, alcoholic solution of t, 10-dioxy-1, 7-dithiacycloo-octane-ad (I). The data obtained are shown in the table. PRI me R I. Production and testing of a photographic emulsion is carried out analogously to Example 7, only. at the stage of preparing the emulsion for poly Y, after the introduction of the sensitizer 1712, compounds of the general formula (M) where x "eu (ll), p-1, x-ac e-CHj-CH; -, are calculated at a rate of 0.1 t per 1 kg of silver, which consists of 1 ml of 0, an alcoholic solution, 7, TZ-Tb-tetanoki 1, E-dithycycloooctadecane-Cu (11) The data obtained are listed in the table. Example 15. The preparation and testing of a photographic emulsion is carried out analogously to example 7, only at the stages of physical ripening immediately after the emulsification process a compound of the general formula (II) is introduced into the reaction mass, where xy (a), at the rate of 2 g per 1 kg of silver, which is 1.5 ml of a 3.3% alcoholic solution of 2,3-benzo-1,4,10-13-tetraoxy-7, 16-dithiacyl octadec-2-yen. These data are shown in the table. As follows from the data obtained in the table, the use of the proposed method of manufacturing a special fine-grained high-resolution bromide-silver photographic emulsion allows to significantly improve the sensitivity, edge sharpness and time of storage of the latent image.

0.6 0.02

1700

1.8 0.95 0.87 0.70

0.65

Claims (1)

METHOD FOR PRODUCING A SPECIFICALLY-GRAIN HIGH-RESOLVING BROWN-SILVER PHOTOGRAPHIC .'EMULSIONS using a chemical sensitizer by emulsification, physical maturation, washing, freezing, chemical aging and heat conditioning , resolution, sharpness of the edge and storage time of the latent image, as a chemical sensitizer use the compound of the general formula (1) or (||) n = and or ι; x-UV-CH ^ -CH - or, which is introduced into the emulsion in an amount of 0.01-5.0 g per 1 kg of silver at the stage of emulsification or physical maturation, or chemical maturation, or preparation for irrigation. '1038919 ripening and preparation for irrigation, as a chemical sensitizer using a compound of General formula (I) or (I I).