DE1147483B - Multilayer photographic material with color components for color development and process for its manufacture - Google Patents

Description

Multilayer photographic material with color components for the colored development and process for its production The invention relates to a Process for the production of photographic color images according to the subtractive Process by color development in halogen silver emulsion layers or in the developer self contained dye images.

It is known that, in order to obtain purple images, dye formers are often used of the pyrazolone series are needed, which however have some disadvantages, which especially from the unfavorable absorption properties of the dye as well also result from the insufficient light and heat fastness of the same.

It is further known that an improvement in these properties can be achieved through the use of 3-amino-5-pyrazolone derivatives. It is however, in this area it is not very easy to obtain descendants of the a in the direction towards the longer waves, the absorption maximum is shifted too much although such couplers are known. The purpose is known through Introduction of a halogen atom or an electronegative group into the phenyl reached in the l-position of these compounds; that now brings another considerable Difficulty for the synthesis with itself. Plus, it's because of the pretty limited Reactivity is not always easy for these products in the manufacture of photographic products Use color films.

According to the invention, color formers are proposed with the absorption maximum of the image dyes from the class of 3-ureido-5-pyrazolones of the following general formula, for the most part considerably shifted towards the longer waves: in which: m, p = 0.1; n = 0, 1, 2, where m, p and n cannot be 0 at the same time; R = a CO -NH group; R1 = an NH group; R2 = a hydrogen atom, an alkyl group, an optionally substituted aryl group or a heterocyclic ring; X = an SO2NH resp.

- NH - SOz group; A = a hydrogen atom, an alkyl, acyl or possibly substituted aryl group or a heterocyclic ring, X and Z = substituents, the one or more acidic solubilizing groups (SO3H, COOH, SO2NH etc.) and can carry one or more diffusion-resistant chains (C7 to Cls).

Particularly interesting results are obtained when n = 0, m = 1 and p = 1.

Compared to known color couplers with heat and lightfast image dyes such absorption maxima at about 540 mp (German patent specification 884151) the new color couplers have various important advantages: greater diffusion resistance, the shortened especially when introducing Chains in the link is useful; the ability to form finer dispersions thanks to the presence the acidic, solubilizing groups; an even higher light and heat resistance, an approximately 250/0 and possibly higher higher responsiveness at the color development and a smaller secondary maximum in the image dyes.

In the following some examples are given for explanation: Dye absorption maximum: 525 mµ Dye absorption maximum: 525 mm Dye absorption maximum: 540 mm Dye absorption maximum: 542 ml 5.CH2 C-NH-CO-NH-CO COOH dye absorption II SO2NH- 1 | maximum: 540 mm CO N y ~ CO N S02NH -0 NH - CO - C17II35 1X SO3H 6. CH2 C-NH-CO-NH-CO-NHSO2NH-O-C9H19 CO N Dye absorption maximum: 526 mm xx II Dye absorption maximum: 537 mol Dye absorption maximum: 525 mg preparation of the intermediate p-chlorosulfobenzene isocyanate 260 g of finely powdered sulfanylic acid are dissolved in 1 distilled water. Suspended o-dichlorobenzene, and at 160 ° C. 4 kg of phosgene are introduced in 40 hours (about 100 g / h) with stirring. The phosgene is removed with dry COl, the dissolved solid substance is filtered and the filtrate is distilled, whereby the useful Preserves product at 132 to 140 "C under 2 mm Hg pressure. Colorless crystals, melting point 53 to 55 "C.

Preparation of the l-phenyl-4-dichlorosulfophenylureido-5-pyrazolone 17.5 g of 1-phenyl-3-amino-5-pyrazolone are dissolved in 200 cc of boiling dioxane, and 22 g of p-chlorosulfophenyl isocyanate are added all at once and then still Lightly cooked for 1 hour. The resulting solution is cooled to room temperature and mixed with a double volume of petroleum ether. The separated precipitate is filtered by washing the filter with petroleum ether.

White dust; Melting point 260 "C.

Example 1 -Phenyl-3- [4'-sulfonamido- (2 "-ethyl-cetylamino-5" -SO3H) -phenyl] -ureido-5-pyrazolone 1 mol of 2-N, N-ethylcetylamino-5- (SO3H) -aniline is dissolved in 6 volumes of anhydrous dioxane and about 150 cc of pyridine are dissolved, and a solution is made dropwise at 90 "C 1.1 mol of sulfochloride according to Example 2 in 5 volumes of anhydrous dioxane were added.

The mixture is heated at a gentle boil for 1 hour and then poured the solution in 501 ice water acidified with HC1. A white precipitate is obtained the filtered, washed with water and after drying by repeated rinsing is cleaned with 40 to 50 "in ethyl alcohol.

40 g of almost white powder are obtained; Melting point 226 to 228 "C (s. Formula 4).

Analysis: N = 10.56% (target value 10.55); S = 7.950 / 0 (setpoint 8.05).

When incorporated in a photographic emulsion and upon exposure and the following development with diethyl-p-phenylenediamine, a purple-colored, very clean image, the main absorption maximum of which is 542 my. The development time can be shortened considerably as compared with that of the normal color coupler. at the given reactivity are also known to be slower, color-forming Developers get good results.

The formulas 3 and 8 are given in the same way Prepared connections.

The dye formers given in formula 7 are from the p-Nitrophenyl isocyanate (Org. Synth., 14, p. 72) by addition to the amino group in the 3-position of the pyrazolone, subsequent reduction (with iron and acetic acid) and Received final condensation.

The dye former according to formula 5 is obtained by reacting the corresponding benzoyl isocyanate with 3-amino-1-phenyl-pyrazolone.

The compound given in formula 6 is obtained by the action of substituted phenylurea to l-phenyl-3-carbaethoxy-amino-5-pyrazolone.

As for compounds 1 and 2, they are prepared in a known manner by acylation of the aminopyrazolone with the appropriate Acid chloride.

If p is 0 in the general formula, then the preparation reaction takes place by addition of the 3-amino-1-phenyl-5-pyrazolone on the aromatic isocyanate containing diffusion-proofing or solubilising groups; It is worked in boiling, anhydrous dioxane, according to the following reaction: The isocyanate is in turn prepared by the action of the phosgene on the corresponding amine, working at 180 ° C. in dichlorobenzene.

Claims (2)

PATENT CLAIMS: 1. Process for the production of photographic color images by color development, characterized in that color former is added to the emulsion or developer with the following general formula: in which: .m, p = 0.1; n = 0, 1, 2, where m, p and n cannot be 0 at the same time; R = a CO - NH group; R1 = an NH group; R2 = a hydrogen atom, an alkyl, an optionally substituted aryl group or a heterocyclic ring; X = a S02NH resp. - NH - SOi group; A = a hydrogen atom, an alkyl, acyl or possibly substituted aryl group or a heterocyclic ring; Y and Z = substituents, the one or more acidic, solubilizing groups (SO3H, COOH, SO2NH etc.) and can carry one or more diffusion-resistant chains (C7 to Cis). 2. Multilayer photographic material for the process according to claim 1, characterized in that it contains a compound according to the following formula as a color former: in which: m, p = 0.1; n = 0, 1, 2, where m, p and n cannot be 0 at the same time; R = a CO - NH group; R1 = an NH group; R2 = a hydrogen atom, an alkyl group, an optionally substituted aryl group or a heterocyclic ring; X = an SO2NH resp. - NH - SOz group; A = a hydrogen atom, an alkyl, acyl or possibly substituted aryl group or a heterocyclic ring; Y and Z = substituents, the one or more acidic solubilizing groups (SO3H, COOH, SO2NH etc.) and can carry one or more diffusion-resistant chains (C7 to C18). Considered publications: German Patent Specifications No. 884 151, 726 611; U.S. Patent Nos. 2,369,489, 2,865,751.