SU107725A1 - The way of feeling panchromatic black-and-white and red-sensitive layer of multi-layer color cinema - Google Patents

Description

In order to sense photographic halogen-silver emulsions containing non-diffusing components of the color display to the red part of the spectrum, some rhocyanic dyes or their mixtures with 9-ethyl-4,5, 4, 5 - dibenzothiocarbocyanines are used. Sensitization with these dyes, however, does not provide sufficient sensitivity, and the use of these mixtures several times beyond the limits of the desired sensing zone.

The described method makes it possible to sense halide silver in the zone that is necessary for the red-sensitive layer of multilayer photographic materials.

Example 1. In a 1 liter of molten, negative bromide-silver emulsion, 150-300 Li of a 0.02% alcoholic solution of 3.9 diethyl-3-p-carboxyethyl-4,5-ben30-5-methoxythiacarbocyanine bromide is injected. After allowing the sensitized emulsion to stand in a thermostat at 40 for 20 minutes. 400 ml of a 3.5% aqueous alkaline solution of 3-sulfo-b-methyl octadecylaminoanilide 1 - hydroxy2-naphthoic acid and 300-45Q ml of water are added. Stabilization is continued for another 20-40 minutes. Then the emulsion is watered on the plate or nlenki.

A highly sensitive photographic material is obtained with a sensitization zone of 540 to 680 mc and a maximum at 655. The photosensitivity of this material behind the red filter is more than 1.5 times higher, compared with the sensitization obtained by the same emulsion, one of the most effective rhodacyanines. Diffusion of the dye into the adjacent emulsion layer containing the purple color component is not observed. Similar results are obtained by combining this sensitizer in a red-sensitive layer with 1- (3-sulfo-4-phenoxyphenium, 1) -3-heptadelylpyrazolone- (5) and the presence in the adjacent layer of one of the blue components derived from 1.2-hydroxy naphthoic acid.

To obtain 3,9-diethyl-3-p-carboxyethyl-4,5-benzo-5-methoxythiacarbocyanine bromide, a mixture of 4.0 g of ethyl methyl sulfate - 2-p-methyl mercaptobutenyl - 4,5-benzo-benzthiazole and 4.2 g | 3 -carboxyethyl-p-toluenesulfonate 2 - methyl - 5 - methoxybenzthiazole is triturated in a mortar, placed in an Erlenmeyer flask, 20 ml of ethyl alcohol and 1.01 2 (1.4 ml) of triethylamine are added. The mixture is stirred, the flask is closed and left at 15-20 ° in the dark place for 12 hours. Then 100 ml of ether are poured, after 2-3 hours the ethereal solution is drained, a few resinous residue is washed with ether and dissolved with heating in 00 ml of ethyl alcohol; 150 ml of a 10% potassium bromide solution are added to the resulting solution. After 3-4 hours, the precipitated precipitate is filtered off, washed with 10 ml of 50% alcohol, 100 ml of water, again 10 ml of 50% alcohol and ether. Weight 3,7-4,0 g; melting point 150-155 °.

For cleaning, the dye is heated with 100 ml of ethanol on the steam bath for 10-15 minutes, cooled and crystallized from 250 ml of ethanol, and brilliant dark green soft prisms with a melting point of 187-190 are obtained in an amount of 2.5 year

The dye can be obtained by condensation under similar conditions or in methanol with 2-methyl-5-methoxy-benzthiazole bromo-carboxyethylate.

Example 2. In a similar way to the previous example, 150-300 ml of a 0.02% alcohol solution of 3,9-diethyl-3- 3carboxyethyl-4, 5-benzo-5-methylthia carbocyanine bromide and after 20- 400 ml of a 2.5% aqueous solution of 3-carboxy-b-methyl octadecylaminoanilide 1 - hydroxy - 4-sulfo-2 - naphthoic acid or (3-sulfo-6-methyl octadecylamino) anilide is added to the incubator of the sensitized emulsion in a thermostat at 40 ° C. 1-hydroxy-2-naphthenic acid or 3,5-d. Dicarboxyanilide para-stearoylaminobenzoyl acetic acid. A photographic material is obtained that is sensitive to the 540-680 pgts zone with a maximum at 655 Sh. The sensitivity behind the red filter of this material is 50% higher than that obtained using rhocyanistin specified in Nimer 1. The diffusion of the sensitizer into the adjacent emulsion layer does not occur. A similar material is obtained using 3,5-dimethyl Zr-carboxyethyl-9-ethyl-4,5benzothiocarbocyanine bromide.

To obtain 3,9-diethyl-3-p-carboxyethyl-5-methylthiacarbocyanine bromide, as in Example 1, to a suspension of 4.0 g of ethylmethylsulfate-2-p-methyl mercaptobutenyl-p-naphtothiazole and 4.0 g of p-carboxyethyl-p-toluenesulfonate 2.5 - dimethylbenzthiazole in 20 ml of absolute ethyl alcohol was added 1.01 g of triethylamine. After keeping the mixture in a protected place for 12 hours. at 15-20 °, 100 ml of ether are poured, the gummy residue is washed with ether, dissolved in 100 ml of ethanol and 150 ml of 10% potassium bromide solution are added. The precipitate that has separated out is filtered off, washed with 50% alcohol, water and ether, dried (weight 3.6-3.9 g; melting point 215-220 °) and crystallized from ethyl alcohol for purification. Weight 2.3 g; melting point 212-215 °, green prisms.

Instead of ethyl alcohol, the reaction can be carried out in methanol or isopropanol.

Example 3. In a similar manner to the previous example, 150-300 ml of a 0.02% alcoholic solution of 3,9-diethyl-3-rcarboxyethyl-4,5-benzo-5-chlorothiacarbocyanine bromide and 400 ml 2, were introduced into 1 g of the emulsion. 5% solution of 3-sulfo-b-methyloctadecylaminoanilide 1 - hydroxy - 2 - naphthoic acid or

N-octadecyl - N (35-dicarboxyphenyl) - amide of 1-hydroxy-2-naphthoic acid. The zone of additional photosensitivity of the photographic material thus obtained is 540 - 680 with a maximum at 650 mc. In terms of the sensitivity of the red filter, this photographic material is only 10-15% inferior to that obtained by sensitization with one of the most effective thiacarbocyanines - 3.3 - di - p - carboxyethyl - 5.5 - dimethoxy-9-ethylthiacarbocyanine.

When sensitizing the emulsion with a mixture of 3.9 - diethyl Zr-carboxyethyl - 4.5 benzo - 5 - chlorothiacarbocyanine bromide (25-30 mg / l) and 3.3 - diethyl - 4.5-diphenyl - 4 - keto - 5 ( 3 ethylbenzthiazolinylidene2-a-propyl ethylidene) thiazolinothiazolocyanine iodide. (10 mg / l) photosensitivity of the photographic material does not differ from that obtained with the last sensitizer. Diffusion of the sensitizer into the adjacent emulsion layer does not occur.

3.9 - diethyl - 3 - p-carboxyethyl 4, 5 - benzo - 5 - chlorothiacarbocyanium bromide is prepared, analogously to examples 1 and 2, by condensation of ethyl methyl sulfate - 2 - p - methyl mercaptobutenyl - p - naphthothiazole (2.0 g) with p-carboxyethyl - p - then. luolsulfate 2 - methyl - 5-chlorobenzthiazole (2.2 g) or the corresponding bromine - p-carboxyethylate in an alcohol solution (10 ml), in the presence of triethylamine (0.51 g) at 20-25 °. The output of 43-46% of theoretical. For purification, the dye is crystallized from ethyl alcohol. Brown-red prisms with a green sheen; melting point 164-166 °.

Example 4. In a similar way to the previous one, as in the example, 150-300 ml of a 0.02% alcoholic solution of 3.9-dethyl-3-rcarboxyethyl-4,5-benzo were introduced into a 1 liter emulsion. - 5-bromothiacarbocyanine bromide and 400 ml of a 2.5% solution of 3-sulfo-6-methyloctadecylaminoanilide 1-hydroxy-4-sulfo-2-paphotic acid, or 1- (3-sulfo-4-phenoxyphenyl) -3-stearoylaminopirozolone ( five).

A significant increase in the sensitivity of the emulsion is observed when a second sensitizer is added: 3,3-diethyl-4,5-diphenyl-4.-Keto-5- (3-ethyl-6, 7-tetramethylene benzothiazolinylidene-2-a-phenylethylidene) thiazo. Lenthiazolocyaniniide, or 3, 3d diethyl - 4,5 - diphenyl - 4 - keto-5 (3 - ethyl - 6 - methoxybenzthiazolinylidene - 2 - ethylidene) thiazolnothiazolocyanine iodide.

The sensitization zone of the obtained photographic material is from 520 to 685 /nf.i with a maximum at 655 mu. Diffuse dyes into the adjacent emulsion layer does not occur. The above dye is obtained in a manner similar to that of measures 1, 2, and 3 when the condensation of ethylmethylsulfate or ethylp-toluenesulfonate-2-p-methylmercaptobutenyl-rnautothiazole with p-carboxyethyl-p-tususulfonato is used. M 2-methyl-5-bromobenzethiazla . Output 50% of theoretical. For purification, the crystal dye from ethyl alcohol (1: 200) is obtained; brown-red prisms are obtained (melting point 187-190).

i i i :) e d LET invented and

The way of sensing panchromatic black-and-white and red-sensitive layers of multi-layer queen-of-film materials that were found in this layer were undifferentiated, and color development components, for example, derivatives of 1, 2 oxynaphthoic acylacetic acids or pyrozolone (5), by introducing a chelating element, 1, 2 oxynaphthoic n-acylacetic acids or pyrozolone (5), by inserting a layer of oxy-naphthoic n-acylacetic acid or pyrozolone (5) by introducing octynaphthoic n-acylacetic acid or pyrozolone (5). layers of thiacarbocyanine dyes or their mixtures with rhodocyanine, dyes, for example, thia-4,5diary, thiacarboxylic or its derivatives, containing in a-polon; nsthiazole residue, substituents, characterized in that, in order to increase the light No. 107725-4 -

non-diffusing, image quality, as component-resistant asymmetric carcinocyanine dye dyes of the general formula:

S C, H, S

where R is alkyl; B - CH3 CH3, C1 or Br; X -

Sn, Sn, ,, soon acid residue.