US2930693A - Photographic materials containing n-substituted phthalimide compounds - Google Patents

Description

UnitedStates atent Q PHOTOGRAPHIC MATERIALS CONTAINING: N- SUBSIITUTED PHTHALIMIDE COMPOUNDS Karl Otto Gauguin, and David WilliamCrichton Ramsay, 'Mahchest'en'En'gland, assignors to lmpen'al Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Application October 30, 1956 Serial No. 619,131

Claims priority, application Great Britain October 19, 1956 4 Claims. (Cl. 96- -56) This invention relates to photographic materials and more particularly to light-sensitive photographic materials containing developers.

In the usual commercial process for developing exposed photographic materials, the photographic materials are passed through a tank containing the developer insolution. With repeated use of the developer solution, the concentration of the developer falls so that the processing conditions vary and it is eventually necessary to add new developer to the tank. Also when multilayer photographic materials are developed in this Way, the developer solution has to ditluse through the upper layers of the photographic materials before it can reach the lower layers so that an' even development of the various layers cannot'be achieved. For example with a photographic mate- I rial containing three dilierently sensitised gelatino silver halide emulsion layers, correct development of the bottom layer can only be obtained by having a high concentration of developer in the developer solution, but under these conditions there is a tendency forthe top layer to be over-developed.

Various suggestions have been made to overcome these dilficulties. For example, it has been proposed to incorporat'e' in the light-sensitive emulsion layers certain developers, or mixtures of developers with certain stabilisers, and, after exposure, todevelop the emulsion layers with aqueous alkali but no such process has yet proved satisfactory in commercial practice.

We havenow found that certain substituted phthalimides, as hereinafter defined, can be incorporated in gelatino-silver halide emulsion layers, and that the emulsion layers, after exposure to light can be developed by treatment with an alkaline solution of hydroxylamine or hydrazine which diffuses readily into the emulsion layers of a multilayer material.

According to our invention we provide a light sensitive gelatino-silver halide emulsion layer which contains a substituted phthalimide of the formula R1 C i 1 RI \C O J wherein R and R are substituted or unsubstituted alkyl radicals or R and R may be joined together or each or both joined to the benzene ring to form with the nitrogen atom a heterocyclic ring, X is hydrogen, an alkyl, substituted alkyl, alkyloxy, substituted alkyloxy, amino or substituted amino radical, and Y is a solubilising group, and wherein the benzene nuclei may carry substituents.

The solubilising group may be for example a carboxylic or sulphonic acid group or a salt of one of these, for example an alkali metal or ammonium salt.

The substitutedphthalimidea may- :be made-iby.1-.-heating.-.

an amine pf the formula t a an,

wherein R R and X have the meaning given above and thephenyl nucleus may carry further.substituents,,with1: phthalic anhydride or a substituted phthalic anhydrideg.. and, where both the amine and; phthalicranhydride-are groups, further treatingthe free from water solubilising product to introduce a water solubilisinggroupr As examples of the substituted phthalimides which may be used inour invention there may be mentioned the compound made by condensing -4-diethylaminoaniline with trimellitic anhydride for example by heating the reagents togetherin boiling glacial acetic acid for 3 hours),the corresponding .aminocompound (X=Nl-l )"formed by nitration and. reduction, -thecompound made by; con- (lensing.4-amino=3 ethoxy-N:N-diethylaniline or-4-amino 3-methyl-N:N-diethylaniline- .with trimellitic anhydride or by condensing.4-diethylaminoaniline or- 4-amino-3- thoxy-NzN-diiethyl'aniline, ,with, 4-sulphophthalic an hydride.

Ina preferred form of our invention the gelatinosilver halideiemulsion nlayer also contains a ,colour coupler.

The emulsions vused .for forming -the-layers ofounirb; vention may be made by simply.,mixing;an- .aqueousisolu tion or dispersion of the substituted phthalim de with a normal gelatino-silver halide emulsiqn prepared in thre known manner and if desiredadding one. onmore sen-1:

least one of the layersis a gelatinoe'silver. halide emulsion layer containing a substituted phthalimide as hereinbefore-- defined, forms a further feature of our invention.

Photographic materials containing the light-sensitive emulsion layers of our invention may be exposed to light in the normal way and then developed with an alkaline solution containing hydroxylamine or hydrazine and this process of development forms a further feature of our invention. If desired other adjuvants for example sodium sulphite and potassium bromide may be added to the developer solution. The material may then be fixed and, when the emulsion layer contains a colour coupler, the developed silver may be bleached.

The invention is illustrated but not limited by the following example in which the parts are by weight:

Example parts of a gelatin-silver iodo-bromide emulsion containing 7.25% of gelatine, 3.35% of silver bromide and 0.05 of silver iodide are stirred and there are added 3 parts of a 0.05% solution in methanol of bis (3 ethyl 5 phenyl benzoxazole 2-) 9-ethy1trimethineyanine iodide (the iodide of the green sensitising dyestuit Rl340 described in B.I.O.S. Final Report No. 1355, page 86). The mixture is stirred at 40 C. for 20 minutes and there are then added 24 parts of a 5% aqueous solution of the sodium salt of 4- (omega-cyan0- acetyl)-oetadecenyl-succinanilide (the colour coupler K6 Parts Sodium sulphite, anhydrous 1 Hydroxylamine hydrochloride 2 Sodium carbonate, anhydrous 30 Potassium bromide 0.5

Water to make up to 1,000 parts. 7

The paper is washed and then transferred to a stop bath of the following composition:

. Parts Sodium thiosulphate 200 Sodium sulphite, anhydrous 2 Sodium acetate Glacial acetic acid 10 Water to make up to 1,000 parts.

The paper is washed and the developed silver is bleached and fixed in a solution of the following composition:

Parts Ferric salt of ethylenediamine-tetra-acetic acid 20 Sodium carbonate, anhydrous 2 Sodium salt of ethylenediamine-tetra-acetic acid..... 10 Sodium sulphite, anhydrous 4 Potassium bromide 10 Sodium thiosulphate 100 Water to make up to 1,000 parts.

The paper is finally washed and dried.

What we claim is:

1. A light sensitive gelatino-silver halide emulsion which contains a substituted phthalimide of the formula:

co 1 N@ N Y co wherein R and R are alkyl radicals, X is selected from the group consisting of alkyl, alkoxy and amino and Y is a solubilising group selected from the class consisting of sulphonic and carboxylic acid groups.

2. A light sensitive gelatino-silver halide emulsion ac cording to claim 1 which contains, in addition to the substituted phthalimide as defined in claim 1, a colour coupler capable of coupling with the oxidation product of a primary aromatic amino developer to form a dye.

3. A photographic material comprising a plurality of layers coated on a support, at least one of said layers being a light sensitive gelatino-silver halide emulsion layer which contains a substituted phthalimide of the formula:

1 oo N-QN Y RI/ \CO wherein R and R are alkyl radicals, X is selected from the group consisting of alkyl, alkoxy and amino and Y is a solubilising group selected from the class consisting of sulphonic and carboxylic acid groups, and which further contains a colour coupler capable of coupling with the oxidation product of a primary aromatic amino developer to form a dye.

4. A 'colour photographic process which comprises imagewise exposing to light a light sensitive gelatino-silver halide emulsion which contains a substituted phthalimide of the formula:

wherein R and R are allcyl radicals, X is selected from the group consisting of alltyl, alkoxy and amino and Y is a solubilising group selected from the class consisting of sulphonic and carboxylic acid groups, and subsequently developing with an alkaline solution of a member of the class consisting of hydroxylamine and hydrazine.

References Cited in the file of this patent UNITED STATES PATENTS 2,137,785 Sanders-Dolgoruki et al. Nov. 22, 1938 2,478,400 Ielley et a1. Aug. 9, 1949 2,706,157 Sainsbury et al. Apr. 12, 1955 OTHER REFERENCES H. Bennett: Concise Chemical & Technical Dictionary, page 26, Chemical Publ. Co., Inc., New York, N.Y., publishers (1947).

Claims (1)

1. A LIGHT SENSITIVE GELATINO-SILVER HALIDE EMULSION WHICH CONTAINS A SUBSTITUTED PHTHALIMIDE OF THE FORMULA: