SU1465865A1 - Method of spectral sensitization of polydispersion bromine-iodine-silver photographic emulsions - Google Patents

Abstract

The invention relates to the production of chemical-photographic materials, in particular, the method of spectral sensitization of polydisperse bromide-containing photoemulsions with an Agl content of 4 mol% and an average microcrystal size of 0.4-0 µm. pI among 6.4-6.6 and pBr 2.8-3. The process is introduced into the emulsion of cation-anionic dyes: salts 3, J- -distilthiazolinocarbocyanan and 3.3 - -di (X sulfopropyl) -4,5,4, 5 -dibenzo-9-eth1thiacarbocyaninebetaine (I) or salt 3, 3 -diethyl-2,2-hino cyanine and 3,3-di- (y-sulfopropyl) - -4 5 4. 3 -dibenzo-U-methylthiacarbocyaninbetin (II) or salt 3,3 - da ethyl-2,2-hinocyash1na and 3,3-di (.J-sulfopropyl) -5,5-dimethoxy-9-ethylthiocarbocyaninebetaine UiiJ, followed by the addition of the dye salt s, 3 -di- (y-sulfopropyl) -4, b - -benzothiaziagashbetaine and decamethylene bis-X-picolini (IV) in the amount of (0.6-1.3) -10-M / M AgHa l. The molar ratio is 1 (11 or III): IV- (2 -2 5) :( O, 6-1.3). These conditions provide better than in the known case, sensitivity (. 25-35%) while maintaining the contrast ratio and density of the veil. 1 tab. S k /) cd 00 O) cd

Description

The invention relates to a method for sensitizing polydisperse bromine with iodine-silver photographic emulsion to the visible spectral range from 450 to 680 nm and can be used in the chemical-photographic industry.

The purpose of the invention is to increase the total and additional photosensitivity while maintaining the contrast ratio and density of the veil.

Example 1. Preparation of 3 3 -di- (Y-sulfopropyl) -4,5-benzo thiadianbetaine salt and decamethylene-bis-β-L-picolini salt.

about 67 g (0.001 mol) of triethylammonium salt 3, h-di- (-suf propropyl) -4, 5 -benzothiacyanine betaine

3

when heated in 30 np of absolute ethanol, 0.24 g (0.0005 mol) of decamethylen-bis- (ob-picoline) dibromide is dissolved by heating n 5 ml of absolute ethanol. The solution of dyes is mixed and boiled for 2 hours. The precipitate that has been washed out is washed with 5 ml of ethyl alcohol. The precipitate is filtered off and crystallized from 190 ml of ethanol. Weight 0.5 g (70% of theoretical value); m.p. 270-272 seconds; woinc im (in ethyl alcohol): extinction coefficient 1.6-10. Found,%: C 58.40; H 8.34;

N 5.53; S 17.46

C.,

Calculated,%: C 58.50; H 8.58; N5,67; S 17.35.

Example 2 (prototype).

A negative polydisperse bromide-silver emulsion is used. Emulsion get single-jet met

In turn, the dye 1 is alternately added to the solution of gelatin; 1 in the amount of tin with potassium iodide are solutions of silver ammine and potassium bromide. The iodide content is 4.0 mol%. The excess of potassium bromide is 30%. The duration of the second ripening is 20 minutes. The separation of the solid phase is carried out by the method of thin-layer separation. For chemical sensitization, 50 ml of a 40% aqueous solution of benzenesulfin sodium, 2 MP of a 10% aqueous solution of potassium rogenous are used; 8 ml of 0.124% sodium thiosulfate solution and 2 ml of 0.08% (by Au) solution of rhodium gold per 1 kg of emulsion. The resulting emulsion consists of Ag Hal crystals with an average size of 0.8 µm and a variation coefficient of 37%. The pBr and pH values of the finished emulsion, respectively, are 2.8 and 6.4. In 1 kg of an emulsion containing 92 g of silver (in terms of metal), 60 ml of a 1% solution of 5-methyl-7-hydroxy-1,3,4-tri2, 0-10 M / M Ag Hal and after 3,3-di - (- sulfopropyl) -4, 5-benzothiacyanine betaine and decamethylene 30 -bis-L-picolini (IV) in the amount of 1, Hal Hal in aqueous solution of the aqueous solution are additionally introduced into the emulsion. Photographic material is obtained with a sensitization maximum of 645 and 460 nm.

35 Example4 (comparative). An emulsion was used as in Example 2, but the duration of its first ripening was 7 minutes. The resulting emulsion contains halogen40 silver microcrystals of average size of 0.4 µm, has, 0 and a pH of 6.6. Dye 11 in the amount of 2 is introduced into 1 l of the emulsion, Ag Hal in the form of 5 M alcohol

45 solution. A photographic material is obtained with sensitization maxima of 565 and 670 nm.

Example 5. The emulsion is sensitized as in Example 4, but

this is kept for 15 minutes

about ,

at 40 ° C and applied to the underlayed glass. Photographic layers are dried and subjected to sensitometric tests. Exhibit the layers on an FSR-41 sensitometer at a color temperature of a 5000K light source without a filter and behind light filters: yellow same-18, orange OS-14, red KS-14, and blue with a maximum transmittance at 450 nm . Show layers in the metol-hydroquinone UE-2 developer for 8 minutes at 20 ° C. The following photographic characteristics are determined: the magnitudes of the total and additional photosensitivity by the point with the density of blackening, + 0.85, the density of the veil (D,) and the coefficient

0 contrast (j). Photographic material is obtained with sensitization maxima of 650 nm and 460 nm.

PRI me R 3. The emulsion is sensitized analogously to example 2, but

25 dye 1 is used in the amount of

2.0-10 M / M Ag Hal and after it, the salt 3,3-di - (- sulfopropyl) -4, 5-benzothiacyanine betaine and decamethylene 30 -bis-L-picolini (IV) in the amount of 1, Ag Hal in vvde aqueous solution. Photographic material is obtained with a sensitization maximum of 645 and 460 nm.

35 Example4 (comparative). An emulsion was used as in Example 2, but the duration of its first ripening was 7 minutes. The polished emulsion contains halogen40 silver microcrystals of average size of 0.4 µm, has 0 and a pH of 6.6. Dye 11 in the amount of 2 is introduced into 1 l of the emulsion, Ag Hal in the form of 5 M alcohol

45 solution. A photographic material is obtained with sensitization maxima of 565 and 670 nm.

Example 5. The emulsion is sensitized as in Example 4, but

azaindolicin and 10 1 ppm of 1% solution; §0 dye II is used in the concentration of pyrocatechin. of 2.010 M / M Ag Hal, and after

A salt of 3,3-di- (| -sulfopropyl) -4.5 is introduced into 1 l of the resulting molten emulsion with stirring,

dye II to the emulsion additionally injected salt of 3,3-di - () g-cdofopropyl) -4, 5 -benzothiacyanine betaine

4, 5 Di-benzo-9-etsh1-thiacarbocyanine-55 decamethylene-bis-o-picolini (IV) betaine and 3,3-diethyl thiazolinocarbo cyanine (I) in the amount of 2.5-10 Ag Hal in the form of 5-10 m alcohol

- M / M

solution. Sensitized emulsion number of 1.0-10 M / M Ag Hal in the form of a 5 10 M aqueous solution. A photographic material with sensitization maxima of 460, 560 and 650 nm is obtained.

dye II to the emulsion additionally injected salt of 3,3-di - () g-cdofopropyl) -4, 5 -benzothiacyanine betaine

 decamethylene bis o picolini (IV)

in the amount of 1.0-10 M / M Ag Hal in the form of a 5 10 M aqueous solution. A photographic material with sensitization maxima of 460, 560 and 650 nm is obtained.

photographic emulsions with an Agl content of 4.0 mol and an average microcrystal size of 0.4-0.8 µm, pH 6.4-6.6, pBr 2.8-3.0 by introducing into the emulsion a cation of a. ionic dyes: salt 3 , 3-diethylthiazolinocarbocyanine and 3, (y cylfo-propyl) -4,5,4, 5 -dibenzo-9 Ethyl Primer (comparative). The emulsion is made analogously to example 4, but dye III is used as a sensitizer in an amount of 2.5-10 M / M Ag Hal as an alcohol solution. A photographic material is obtained with sensitization maxima at 564 and 626 nm.,. ,, ... „.,, -, 7- Example. An emulsion of sensitization of thiacarbocyaninebetaine (I) or salts is lysed as in Example 6, but3,3-diethyl-2,2-chinocyanine and 3.3 - di- () (-sulfopropyl) -4,5,4, -5 - Dibenz o-9-3 tilthiacarbocyaninebetaine (II) or, 3-diethyl-2,2-quino-15 cyanine and 3, h -di- (| -sulfopropyl) - -5,5-dimethoxy-9-ethylthiacarbocyanine betaine ( III), distinguished by the fact that, in order to increase the total and additional photosensitivity after dye III, dye IV is additionally introduced into the emulsion in an amount of 0.6 to 10 M / M Ag Hal in the form of an aqueous solution. A photographic material is obtained with sensibi maxima — I Livadia 465, 564, and 625 nm.

The results of photographic tests of samples of the material obtained

Scientific Research Institute Milazepucuid, nvjji j, - .-.

in examples 2-7, are given in the table. 20 values while maintaining the coefficient ...... "ttch H CSTSPTT /% h GGP 1 GT PO RI.L f TI HV3

From the data of the table it follows that the use of the anticipated method of seabilitation with the use of a sensitizer — salt 3, g-di- (| p-sulfo-propyl) -4, 5-benzothiacyanine betaine and decamethylene bis-ab-picolini, allows to increase the total and additional photosensitivity by 25-35% while maintaining the contrast ratio and density of the veil.

invention of the method of spectral sensitization of contrast and density of the veil, the dye is added to the emulsion after these dyes - salt 3,3-di (J-sulfopropyl) -4, 5-benzothiacyanine betaia and decamethylene bis-v-picolini of formula IV

3D

 (SNG) „- K

sh.

((

in the amount of (0.6-1.3). 1 CG M / M Ag Hal, with a molar ratio of I

SPOSOO SPECTRAL i.en.nun ..- in - с. / П A-l Ч

tion of polydisperse bromide-silver 35 (™ III): IV - (2-2, b). (, and, p i, j ;.

65865

photographic emulsions with an Agl content of 4.0 mol and an average microcrystal size of 0.4-0.8 µm, pH 6.4-6.6, pBr 2.8-3.0 by introducing into the emulsion a cation of a. ionic dyes: salt 3 , 3 -diethylthiazolinocarbocyanine and 3, (y methylfo-propyl) -4,5,4, 5 -dibenzo-9 Ethyl,. ,, ... „.,, -, 7th thiacarbocyaninebetaine (I) or 3,3-diethyl-2,2-chinocyanine salts and 3,3 0 salts while maintaining the coefficient“ xh. “Tth CHTPTTT /% h GGP 1 GT PO RI.L f TI HV3

the contrast and density of the veil, the dye is added to the emulsion after these dyes - salt 3,3-di (J-sulfopropyl-25-pil) -4, 5-benzothiacyanine betaetium and decamethylene-bis-vL-picolini of formula IV

 (SNG) „- K

sh.

((

in the amount of (0.6-1.3). 1 CG M / M Ag Hal, with a molar ratio of I

- in - с. / П A-l Ч

Claims (1)

Claim Method for spectral sensitization of polydisperone silver bromide-silver photographic emulsions with an Agl content of 4.0 mol% by an average microcrystal size d _c p 0.4-0.8 μm, pH 6.4-6.6, pBr 2.8-3.0 to the emulsion of cation-anionic dyes: salts of 3,3 * -diethylthiazolinocarbocyanine and 3,3 * -di- (G-sulfopropyl) -4,5,4 ', 5 * -dibenzo-9-ethylthiacarbocyanine betaine (I) or salts 3, 3 * -diethyl-2,2'-chinocyanine and 3.3 ^G -di - (^ - sulfopropyl) ~ 4.5.4 ^G , 5'-dibenz o-9-ethylthiacarbocyanine betaine (II) or salts of 3.3 * -diethyl-2,2-quinocyanine and 3,3-di-Q-sulfopropyl) -5,5-dimethoxy-9-ethylthiacarbocyanine betaine (III), because of the fact that, in order to increase the overall and additional photosensitivity while maintaining the contrast coefficient and density of the veil, an additional dye is added to the emulsion after these dyes - salt 3.3 -di (J-sulfopropyl) -4 ', 5-benzothiacyanine betaine and decamethylene-bis-o4 ~ picolinium of formula IV | _ J (CH ₂ ) jSO3 (CHj1S0 ₃ in the amount of (0.6-1.3) · 1 (Г ⁴ M / M Ag Hal, in a molar ratio of I (II or III): IV = (2-2.5) :( 0.6-1.3). <M <G O СО Γχ. σ \ CM CM - - f about l Λ Λ "To * • h Ltd oh oh about 1 With Gh> 1L <± G * about 1 "B "H • h • h l 1 With with with WITH SM with " 1 " " 00 G * x <t O about 1 "to *1 "H ** "h "H 1 With with with СО СО with 1 " 1 " with Gh Gx U0 Gh 1 • b • h • h • H V4 "TO 1 with With With with him cm . 1 1 t .TO eleven 1 J nJ 1 About about about oh oh about 1 1 1 & t CM about With 00 -J with 1 1 1 YU Joint venture <r - “ 1 1 1 about • TO 1 [ about d f 1 F and 1 1 Ohm ώ ί 1 & ( 1______________ 1 1 1 I Si . t 1 f 1 l § I j Ohm • ! 1 FROM 1 1 I 1 ----------1