CS239404B1 - Method of spectral sensitization of halogen silver black and white and chromogenic induced photographic emulsions - Google Patents

Abstract

The subject of the invention is orthochromatic and panchromatic sensitization of silver halide negative black and white and color highly sensitive photographic materials without addition and with addition of color-forming components, single-layer and multilayer, prepared by classical methods or by the solid phase separation method using a combination of two orthochromatic and one panchromatic sensitizer. Variously substituted monomethicyanines and variously substituted symmetrical Si unsymmetrical imidacarbocyanines are used as orthochromatic sensitizers and symmetrical or unsymmetrical thiacarbocyanine, substituted in the 9-position by an alkyl group, also substituted in the 6-position of the benzthiazole nucleus by an alkyl group, is used as panchromatic sensitizer. This achieves an increase in sensitivity of 200 to 280% of the original value of the unsensitized silver halide emulsion with sensitization maxima of 520 to 530 nm, 560 to 570 nm, 620 to 630 nm and a sensitization range of 640 to 650 nm.

Description

The subject of the invention is the orthochrometic and panchromatic sensitization of halogen-silver negative black-and-white and chromagen-induced photographic materials with or without the addition of color-forming components, monolayer and multilayer, carried out by conventional methods or solid phase separation methods.

The spectral sensitizers used hitherto have been less effective and with less suitable spectral sensitivity distributions for the desired sensitization of the orthopanchromatic region of the spectrum. A further disadvantage of the spectral sensitizers used hitherto is the tendency of some sensitizing dyes to form an undesirable veil, their inappropriate sensitizing range or, in combination, the mutual desensitizing effect.

The essence of the invention is to improve the spectral sensitivity in the orthochromatic and panchrometic regions of the spectrum of silver-black and white chromium-plated emulsions with or without color-forming components, so as to approach the sensitivity curve to human eye colors addition of color-forming components, monolayer and multilayer, carried out by classical or solid-phase separation methods by combining two orthochromatic sensitizers of formulas I, 11 and a panchromatic sensitizer of formula III:

(I) where

R, R are independently alkyl having 1 or 2 carbon atoms, kerboxyalkyl having 1 or 2 carbon atoms, sulfoalkyl having 3 or 4 carbon atoms, sulfatoalkyl having 1 or 2 carbon atoms;

represents a hydrogen atom, a methyl group, a methoxy group;

represents a hydrogen atom, a methyl group, a methoxy group; ethoxy, halogen and is an anion,

(II) where

R, r 'independently represent a saturated or unsaturated alkyl group having a total carbon number of 1 to 3, a kerboxyalkyl group having a total carbon number of 1 or 2, a sulfoalkyl group having a total carbon number of 3 or 4, a sulfatoalkyl group with a total carbon number of 2

R ⁴ , R ⁴ are hydrogen or halogen; \

5

R, R are halogen;

R @ 1, R @ 7 are saturated or unsaturated alkyl having a total number of carbon atoms of 1 to 3, phenyl and

X ^- represents anion, (III)

where

R ¹ , R ¹ are independently alkyl saturated or unsaturated with a total number of carbon atoms of 1 to 3, carboxyalkyl group with a total number of carbon atoms of S 1 -A 1 or 2, sulfealkyl group with a total number of carbon atoms of 3 or 4; ;

R, R are independently hydrogen, methyl, methoxy

X 'means anion and

A is methyl or ethyl

An advantage of the invention is to obtain a material with a sensitivity gain of up to 280% of the original value.

He did

A bromo-silver photographic emulsion containing 4 mol% silver iodide and 38 g silver per kg emulsion was prepared. Chemical maturation brought to the optimum sensitometric values by sensitization with complex gold compounds. 10 kg of anhydro-1'-ethyl-3 (beta-carboxyethyl) -5,6'-dimethoxythia-2'-cyanine hydroxide, 5-15 g of sodium anhydro-1, are added to 1 kg of the emulsion prepared so far, 1-diethyl-3,3-bis-γ-sulfepropyl) 5,5, 6,6'-tetrachloro-imidacarbocyanine hydroxide, 15 to 25 mg of anhydro-3,3'-bis- (gamma-sulfopropyl) - 6,6'-dimethylthiacarbocyanine hydroxide. The emulsion is stabilized with 0.3 g of 4-oxo-6-methyl-1,2,4-triazolo- (2,3a) -pyrimidine and, after stirring for 1 hour, is poured onto a film mat. A highly sensitive orthopanchromatic material is obtained wherein the sensitivity gain is 240 to 280% of the spectral non-sensitized emulsion value. The maximum spectral sensitivity is approximately 520 nm, 570 nm, 620 nm with a sensitization range of 640 to 650 nm.

Example 2

Prepared solutions of 10 to 30 g / kg of anhydro-1'-ethyl-3 (gamma-sulfopropyl) -5 emulsion were added to the prepared 3-molybdenum-silver emulsion containing 4 mol% silver iodide and a silver content of 38 g / 1 kg of emulsion. - methoxy-6'-methylthia-2'-cyanine hydroxide, 5 to 15 g per kg of anhydro-1,1'-diphenyl-3,3 * - (4-sulfobutyl) -5,5 'sodium salt emulsion, 6,6'-tetrachlorimidakarbocyanin hydroxide and 15 to 25 g per 1 kg of emulsion anhydro-bis-3,3 '- (4S> ifobutyl) -6 _s 6'-dimethoxythiakarbocyaninvhydroxidu. Chemical sensitization is carried out again using complex gold compounds to the optimum sensitometric values. The emulsion is stabilized with 0.3 g of _{4-oxo-b-methyl-1>} 2,4-triazolo (2,3-a) pyrimidine. A sensitivity increase of 200 to 260% of the original value of the spectral non-sensitized emulsion is obtained. Max. Sensitization cce 520, 560 to 570, 30 with a sensitization range of 640 to 650 nm.

The method of spectral sensitization of helogenic silvery and chromogenic induced photographic emulsions beside and with the addition of color-forming components, using one or more layers, carried out by classical Si methods of solid phase separation OF.

Claims (1)

BACKGROUND OF THE INVENTION (1) wherein R ¹ , R ¹ are independently alkyl of 1 or 2, carboxyalkyl of 1 or 2, a sulfoalkyl of 3 or 4, sulfonoyl of 1 or 2, r 2 is hydrogen , methyl, methoxy, R1 represents a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, a halogen and a X 'is an anion, and of formula II wherein R, r 'are independently saturated or unsaturated alkyl having 1 to 3 carbon atoms, carboxyalkyl having 1 or 2 total carbon atoms, a sulfoalkyl having 3 or 4 total carbon atoms, sulfatoalkyl having 1 or 2 total carbon atoms, R ⁴ , R ⁴ are hydrogen or halogen, R 1, R 2 are halogen, r ⁶ , R ⁷ are saturated or unsaturated alkyl having a total of carbon atoms of 3 or 3, phenyl and X 'means an anion, and one panchromatic sensitizer of formula III (III) ► X. where R ¹ , R ¹ are independently alkyl saturated or unsaturated with total carbon atoms of 1 and 13, carboxyalkyl total of 1 or 2, sulfoalkyl of 3 or 4, sulfatoalkyl of 1 or 2, B ² , are independently hydrogen, methyl, methoxy, anion, and methyl or ethyl.