DD147731A1 - COLOR PHOTOGRAPHIC MATERIAL WITH POLYMER COLOR COUPLERS - Google Patents

Abstract

The invention relates to a color photographic material based on halogen silver emulsions. The aim and the object is to obtain color images with high color yield, high sheen and low fog with a halogen silver material containing in at least one layer a diffusion-resistant polymeric color coupler, which little or no influence on the viscosity of the emulsion by low interaction. The color couplers correspond to the general formula in which: R & ind1! Hydrogen, alkyl, alkoxy, alkoxycarbonyl, aryl, aryloxy, aryloxycarbonyl, halogen, nitrile; R & ind2 !, R & ind3! Hydrogen, alkyl; R & ind4 !, R & ind5! Hydrogen, alkyl, halogen; R & ind6! Alkyl, substituted alkyl, aryl; R & ind7 !, R & ind8! Hydrogen, alkyl, substituted alkyl, aryl; K is a color-forming group containing an optionally substituted acylacetanilide, 1-aryl-pyrazolone (5), 1-naphthol or phenol structure; and X, Y, Z are broken numbers with the sum of 1.

Description

VEB Filmfabrik Wolfen Wolfen, November 16, 1979

PN 790 IVk

Int.Cl. ² G 03 C 7/32

7/26 1/06

- <- 217579

Color photographic material with polymeric color couplers

Application field of this invention is fi njj_u_n_g_

The invention relates to a color photographic material containing polymeric photographic couplers in the silver halide emulsion.

pj ^ J: j3_r is * A K-4 ^Θ ..Γ- b ^ ka ⁿⁿ * .. ^{e n} . * ^{E, c} _n ^{n, n} ^, ^{cn. s} solutions for the establishment of couplers in the binder layers of photographic materials have been proposed various ways to diffusion-resistant color couplers store in the photographic individual layers. For example, it is possible to work in a heterogeneous phase and to emulsify the solution of hydrophobic color couplers in a low-boiling organic solvent, optionally with the addition of a low-volatility, high-boiling organic, so-called coupler solvent, in the hydrophilic binder. Or you can work in a homogeneous phase and add the couplers, which were rendered alkali-soluble by sulfo or carboxyl groups and provided with diffusion-inhibiting, long-chain, aliphatic radicals, the halide silver emulsion.

Besides these two mentioned methods, numerous proposals have been made to improve the diffusion resistance of the

- 2 -

Color coupler to achieve by linking with polymeric compounds.

The incorporation of polymeric couplers in hydrophilic colloidal systems, such as gelatin, has important advantages over the introduction of nonpolymeric couplers. "A particular advantage of polymeric couplers is the production of photographic material with thin emulsion layers, which allows extremely good and sharp image reproduction. On the other hand, the advantage lies in the fact that the polymeric color coupler can replace a part of the binder, since they have protective colloid properties. Thus, Z ₉ B, described in DE-PS 1 073 307 reaction products of amino-containing monomeric coupler substances with copolymers of maleic anhydride and styrene. The subject of DE-AS 1 123 913 are also reaction products of maleic anhydride / N-vinylpyrrolidone copolymers with amino-containing monomeric coupler substances,

These polymeric color couplers in practice show various disadvantages which are closely related to their alkaline incorporation (hydrophilicity of the couplers). The couplers can not be added to the emulsion in the required concentration because presumably there is limited miscibility due to the lack of constitutional relationship to gelatin. As a result, too little color intensity results. On the other hand, they have the property of increasing the viscosity of the photographic emulsion in an intolerable manner, thereby complicating the casting. By adding water you can adjust the viscosity to the optimum value, but the energy expenditure of the evaporation is considerable «

~~ ³ " 9 1 ys 79

Object of the invention

The object of the invention is to find a color photographic material which provides color images with high color yield, high sharpness and low fog in silver halide emulsions with polymeric color couplers.

Presentation of the essence the invention

It is an object of the invention to provide a color photographic material containing one or more polymeric color couplers which can be incorporated in the required concentration in the silver halide emulsion, the viscosity of the emulsion by little interaction little or not and provide color images of required color intensity.

According to the invention, this object is achieved in that the photographic material based on silver halide emulsions in at least one layer as a color coupler a diffusion-resistant carboxylgruppenfreie- or low-carboxyl compound, wherein at least 70 % of the carboxyl groups present are esterified, the general formula

in the

Hydrogen, alkyl, alkoxy, alkoxycarbonyl, aryl, aryloxy, aryloxycarbonyl, halogen, nitrile

Hydrogen, alkyl hydrogen, alkyl, halogen

 - 4 -

F? Alkyl, substituted alkyl, aryl 6

R R is hydrogen, alkyl, substituted alkyl, aryl

K - a color-forming group which has an optionally substituted acylacetanilide, 1-arylpyrazolone (5), 1-naphthol or phenol structure,

X, Y, Z are broken numbers with the sum 1

mean, contains «,

For the preparation of the photographic material according to the invention, the polymeric photographic color coupler in a low boiling organic solvent (z _e as ethyl acetate, butyl acetate, methanol) or with the addition of a high boiling organic solvent (z _e as dibutyl phthalate, Dikresylphosphat, benzyl alcohol), or only in high-boiling organic solvents and in the binder, for example, the gelatin, with aer they are well tolerated, emulsified «Since they themselves already have good film-forming properties, one comes with little gelatin _e It is therefore possible, the same amounts of coupler units in essential to accommodate thinner layers than when using low molecular weight couplers «

100 g of a Silberbrotnid «emulsion _for the per kg of emulsion containing 90 g of gelatin and a 52 g of silver nitrate equivalent amount of silver halide are diluted with 100 ml of water. 70 g of a solution containing 0.006 mol of a polymeric yellow coupler prepared according to DE-PS 1 073 307 and 4 g of gelatin are added to the emulsion formed, with stirring.

After adding the usual additives, such as _o stabilizers, wetting agents and hardeners, the required amount of dist. Water added to get 400g. This emulsion is applied to a cellulose acetate support, dried and coated with a protective layer.

Material_B

80 g of a silver bromide emulsion containing per g of emulsion 90 g of gelatin and a 62 g of silver nitrate equivalent amount of silver halide are mixed with 100 ml of dist. Diluted with water. To the resulting emulsion are added, with stirring, 70 grams of a dispersion which esterifies 4.4 grams of a styrene-maleic acid copolymer coupler and p-aminobenzoylacet-o-chloroanilide, corresponding to 0.006 mole of monomeric color coupler, containing 2 grams of gelatin. After adding the usual additives, such as Stabilizers, wetting agents and hardeners ", the required amount of dist. Water is added to obtain 400 g.

This emulsion is applied to a cellulose acetate support, dried and coated with a protective layer.

After drying, the materials A and B are exposed through a continuous wedge and a step wedge and then developed for 15 minutes at 26 ⁰ C in a developer bath of the following composition:

N, N-diethyl-p-phenylenediamine sulfate hydroxylamine sulfate

Sodium Hexametaphosphate Anhydrous Sodium Sulfite Anhydrous Potassium Carbonate Potassium bromide

Water to fill up

2-4 G 1-2 G 3-5 g. 1-3 9 70-90 G 1-3 G 1 liter (PH: 10.9 * 0.1)

The developed materials are watered for 1/2 minute at 12-15 ⁰ C and then treated for 5 minutes at 19-21 ⁰ C in a bath of the following composition:

anhydrous sodium sulfite 6-9 g

Sodium acetate 10-20 g

Glacial acetic acid 15-35 ml

Potassium aluminum sulfate-12 »water 20-30 g

Sodium thiosulfate 100-150 g

Water to fill up to 1 liter

(pH: 4.2 * 0.2)

The material is rinsed with water for 5 minutes and treated in a bleaching bath of the following composition:

Potassium hexacyanoferrate (III) 70-120 g

Potassium bromide 12-20 g

Potassium dihydrogen phosphate · 4-7 g

Disodium hydrogen phosphate-12-water 3 ~ 6 g

Water to fill up to 1 liter

(pH: 6.2 * 0.2)

After bleaching, the materials are spooled with water for 5 minutes and fixed in an aqueous solution of 100-200 g of sodium thiosulfate per liter »

After 15 minutes of final spooling, the material is dried.

A yellow-colored wedge image is obtained. Some photographic results are shown in the following table «

TO r> Λ I IQ ö ω w α. λ. w

Material casting thickness gamma relat. Em- D- D.

____ Z. pfindl ichk. ^{max. min}

A 7.5 n _e meßb "n, meßb _a 1.0 0.38

B 5.3 1.79 5.9 3.0 0.14

The above results show that using the polymeric couplers of the present invention, substantially thinner layers are obtained, as well as first-time measurable photographic values over the prior art, which also allow for application over conventional color couplers.

Claims (1)

invention claim ^R 2 ' ^R 3 R ,. R Hydrogen, alkyl, alkoxy, alkoxycarbonyl, aryl, aryloxy, aryloxycarbonyl, halogen, nitrile, Hydrogen, alkyl,
Is hydrogen, alkyl, halogen, alkyl, substituted alkyl, aryl, hydrogen, alkyl, substituted alkyl, aryl, a color-forming group having a given substituted acylacetanilide, 1-arylpyrazolone-CS), 1-naphthol or phenol structure, broken numbers with the sum 1 mean are included »