US3068097A

US3068097A - Developers for color photography containing sulfite ester polymers

Info

Publication number: US3068097A
Application number: US97446A
Authority: US
Inventors: Judith A Schwan; Peter P Chiesa
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1961-03-22
Filing date: 1961-03-22
Publication date: 1962-12-11
Anticipated expiration: 1979-12-11
Also published as: BE615409A; GB978624A

Description

United States Patent Ofilice 3,h8,097 Patented Dec. 11, 1962 This invention relates to color photography, and more particularly, to color developer addenda for increasing the color density to color fog ratio in processed color photographic materials. Preferred embodiments of the invention concern developer addenda useful in increasing the cyan density to cyan fog ratio in reversal color systems.

Multilayer photographic elements used for color photography usually have at least three selectively sensitive emulsion layers coated on one side of a support. For example, the uppermost layer is generally blue-sensitive, the next layer is generally green-sensitive, and the layer adjacent to the support is generally red-sensitive. Between the blueand green-sensitive emulsion layers typically is a filter layer for absorbing blue radiation which may be transmitted through the uppermost blue-sensitive layer. Such multilayer photographic elements can also, of course, have other interlayers for specialized purposes. Such multilayer materials have previously been described in the art, reference being made to Mannes US. Patent No. 2,252,718, issued August 19, 1941.

In processing exposed reversal color systems the exposed material is given a conventional black-and white development to produce a black-and-White image and a second exposure or exposures through separation filters followed by at least one additional development in a color developer for producing a colored image, the colored image bearing a complementary relationship to the the region of the spectrum to which the photographic emulsion layer has been differentially sensitized. One of the problems in the color development of such systems is connected with the first color development, namely, the cyan development of the red-sensitized layer. The desired maximum cyan dye density must be obtained in the exposed regions With a minimum of cyan fog in the unexposed areas such as cyan development in the greenand blue-sensitive layers which have not been re-exposed. Attempts to increase the maximum cyan density obtainable, i.e. D-max., such as by prolonged cyan development, are generally accompanied by an increase in cyan fog. In addition, all exposed silver halide grains from the first re-exposure must be completely developed or reduced before subsequent color developments to avoid yellow or magenta contamination of the cyan layer. For these reasons it is highly desirable to employ developer addenda which give improvement in the cyan D-max./fog ratio, whether this improvement comes from an increase in D-max. or in decrease in fog.

It is therefore an object of this invention to provide novel color developer addenda to increase color density in the processing of exposed color photographic elements.

It is another object of this invention to provide novel developer addenda suitable for improving the cyan D- max/fog ratio in reversal color systems.

it is another object of this invention to provide novel developers which contain color-forming materials or couplcrs and novel color development accelerators suitable for use in processing multilayer reversal color systems.

it is likewise an object of this invention to provide a new process for processing color photographic elements with developer addenda that give maximum color density with a minimum of color fog, particularly in the redsensi-tive layer.

These and other objects of the invention will be apparent from the description and claims which follow.

The developer compositions of the invention are alkaline aqueous compositions comprising a typical arylene amine color developing agent and a sulfite ester polymer, such sulfite ester polymers being novel addenda to color developing compositions.

The sulfite ester polymers of the invention consist essentially of the recurring structural unit OSOX- wherein the substituent X is a polyoxyethylene radical having the structure wherein the substituent X is a polyoxyalkylene radical as described above. Typically this reaction is carried out by slowly adding substantially equal molar proportions of thionyl chloride to a polyalkylene glycol in a suitable inert organic solvent such as benzene and thereafter refluxing the resulting reaction mixture for a few minutes. The

"resulting polymeric sensitizer can then be readily separated from the reaction mixture by distilling off the solvent. Further purification of the polymer can be effected, if desired, by conventional methods. Polyalkylene glycols are well-known compositions of commerce and can be prepared from alkylene oxides such as ethylene oxide, 1,2-propylene oxide, 1,3-butylene oxide and the like which have in turn been prepared from the corresponding unsaturated hydrocarbon. Typical polyalkylene glycols that can be employed to prepare the present sulfite ester polymers include:

(a) Diethylene glycol, HO(CH CH O) H (b) Triethylene glycol, HO(CH CH O) H (c) Tetraethylene glycol, HO(CH CH O) H (d) Tripropylene glycol, HO(CH CH CH O) H (e) Dibutylene glycol, HO(CH CH CH CH O) H and the like.

Typical color developers useful in combination with the sulfite ester polymer addenda of the invention are the well-known color-forming developers that have previously been described in the art. The color-forming developers that have been found especially useful in our invention comprise aromatic primary amines containing an amino (substituted or unsubstituted) or hydroxyl radicals. Excellent results are obtained with p-phenylenediamines and substituted derivatives thereof containing a primary amino radical. Typical of such color-forming developers that can be suitably employed in combination with the sulfite ester polymers of the invention are the -August 28, 1951.

aoeapav sulfonamide substituted p-phcnylenediamines disclosed by Weissberger in U.S. Patent 2,548,574, issued April 10, 1951, and the substituted p-phenylenediamines disclosed by Weissberger et al. in US. Patent 2,566,271 issued Other phenylenediarnine color-forming developers can be employed to like advantage in the developing process of the invention.

The novel developer compositions of the invention are alkaline aqueous compositions. In addition to the sulfite ester polymer addenda of the invention and a color developer, the developer compositions of the invention also include such usual addenda as alkali metal sulfites and the like.

Our invention is primarily directed to the development of ordinarily employed gelatino-silver-halide developingout emulsions such as gelatino-silver-chloride, gelatinochlorobromide, gelatino-chloroiodide, gelatino-chlorobromiodide, gelatino-bromide and gelatino-bromiodide developing-out emulsions. The photographic silver halide emulsions that can be developed with the subject novel developer compositions can be prepared according to known methods, such as those described in Hewitson et al. US. Patent 2,618,556, issued November 18, 1952, for example. Of course, emulsions prepared by other methods can be used to equal advantage in the subject invention. Photographic silver halide emulsions that can be developed with the subject developer compositions can contain common emulsion addenda as chemical sensitizers such as sulfur sensitizers, gold compounds, azaindene compounds and others such as are disclosed in US. Patents 2,540,085, 2,597,856, 2,597,915, 2,716,062, 2,937,089 and in others. V

The subject sulfite ester polymers can be employed in' color-developing compositions containing color couplers. Such compounds usually belong to one of three widely known types, i.e. pyrazolone couplers, phenol coupers and open chain ketomethylene couplers which combine with developer oxidation products to produce magenta, cyan and yellow images respectively. Our invention is particularly useful in reversal color photographic processes wherein the color-forming compound or coupler is incorporated in one of the developing baths. Colorforming compounds or couplers which are soluble in the strongly alkaline developing aqueous compositions are well-known to those skilled in the art. The developer compositions of the invention can also be utilized to process photographic emulsions having couplers incorporated therein.

Typical color-forming compounds or couplers which are useful in color photography, according to our invention, include the following:

COUPLERS PRODUCING CYAN IMAGES l-hydroxy-2-(N-isoamyl-N-phenyl)naphthamide l-hydroxy-2-(N-p-sec. amylphenyl)naphthamide 8-hydroXy-1'm-naphthoyl-l,2,3,4-tetrahydroquinoline 2-lauryl-4-chloropheno1 1-naphthol-Z-carboxylic-a-napthalide l-naphthol--sulfo-cyclohexylamide 5-phenoxyacetamino-l-naphthol 5 -;3phenylpropionylarninol-naphthol Monochlor-S-(N-y-phenylpropyl-N-p-sec.-amylbenzoylamino) -1-naphthol 2-acetylamino-5-methylphenol 2-benzoylamino-3 ,5-dimethylphenol 2-u(p-tert. amylphenoxy)-n-butyrylamino-5-methylphenol 6-{y-{4- 2,4-di-tert. amylphenoxy-butyramido] phenoxy} acetamido}-2,4-dichloro-3-methylphenol lhydroxy-2- 5- 2,4-di-tert. amylphenoxy) -n-butyl] naphthamide 2% (p-tert. amylphenoxy) -n-butyrylamino-4-chloro-5- methylphenol 2-(p-tert. amylphenoxy-p-benzoyl) amino-4-chloro5- methylphenol 2- 4 -tert. amyl-3 '-phenoxybenzoylamino -3 ,5 -dim ethyll-phenol 2-phenylacetylamino-4-chloro-5-methylphenol 2-benzoylamino-4-chloro-5 -methy1phenol Z-anilinoacetylamino-4chloro-S -rnethylpheno1 2- [4,3 4-tert. amylphenoxy)benzoylamino1benzoylamino-4-chloro-5-methylpheno1 Z-p-nitrobenzoylamino-4-chloro-5 -methylphenol 2-m-aminobenzoyl-4-chloro-S-rnethylphenol Z-acetamino-4-chloro-S-methylphenol 2(4'-sec. amylbenzamino)-4-chloro-5-methylphenol 2 (4'-n-amyloxybenzamino -4-chloro-5-rnethylphen ol 2 (4-phenoxybenzoylamino phenol 2 4"-tert. amyl-3 -phenoxybenzoylamino phenol 2- u- 4-tert. butylphenoxy) propionylamino] phenol 2-[a-(4'-t61l. amyl) phenoxypropionylamino]phenol 2- [N-methyl-N-(4"-tert. amyl-3 -phenoxybenzoylamino) 1 phenol 2-(4-tert. amyl-3-phenoxybenzoylamino) -3-methyl-1- phenol 2-( 4-tert. amyl-3 '-phenoxyb enzoylamino -6-methyl- I- phenol 2- (4"-tert. amyl-3'-phenoxybenzoylamino) -3 ,6-dimethylphenol 2,6-di(4"-tert. amyl-3'-phenoxybenzoylamino)-1-phenol 2-oc-(4'-tert. amylphenoxy butyrylaminol -phenol 2 (4"-tertv amyl-3 '-phenoxybenzoylarnino) -3 ,S-dimethyllphenol 2- a- (4'-tert. amylphenoxy )-n-butyrylamino] -5-methyl-1- phenol 2 4"-tert. amyl-3 '-phenoxybenzoylamino -4-chloro lphenol 3- a- (4'-tert. amylphenoxy) -n-butyrylamino] -6-ch.oro

phenol 3-(4"-tert. amyl-3 -phenoxybenzoylarnino phenol 2- oz- 4'-tert. amylphenoxy) -n-butyrylamino] -6-chlorophenol 3-[a-(4-tert. amylphenoxy)-n-butyrylamino]-4-chlorophenol 3 a:- 4'-tert. amylphenoxy) -n-butyrylamino] -5'-chlorophenol 3 oc- 4-tert. amylphenoxy) -n-butyrylamino] -2-chlorophenol 2-a-(4'-te1t. amylphenoxybutyrylamino) -5-chlorophenol 2-(4"-tert. amyl-3-phenoxybenzoylamino)-3-chloropheno1 S-benzene sulfonamino-l-naphthol 2,4-dicl1loro-5-benzenesulfonaminol'n aphthol 2,4-dichloro-5 -(p-toluenesulfonamino -1-naphthol 5-( 1,2,3 ,4-tetrahydronaphthalene-6-sulfamino) -1-naphthol 2,4-dichloro-5- 4bromodiphenyl-4-sulfonamino l naphthol 5'- quinoline-S-sulfamino l-naphthol Any of the acylaminophenol couplers disclosed in Salminen and Weissberger US. Patent 2,423,730, dated July 8, 1947, can be used as couplers for the cyan image, e.g.

l -NHC o-on-oQ-onn NBC o-on-oQ-orsm etc.

COUPLERS PRODUCING MAGENTA IMAGES l-p-sec. amylphenyl-3-n-amyl-5-pyrazolone 2-cyanoacetyl-5-(p-sec. amylbenzoylamino)coumarone 2-cyanoacetylcoumarone-S-(n-amyl-p-sec. amylsulfanilide) Z-cyanoacetylcoumarone-S-(N-n-amyl-p-tert. amylsulfanilide) 2-cyanoacetylcourmarone-5-sulfon-N-n-butylanilide Z-cyanoacetyl-S-benzoylamino-coumarone 2-cyanoacetylcoumarone-5'-sulfondimethylamide 2-cyanoacetylcoumarone-S-sulfon-N-methylanlide 2-cyanoacetylnaphthalene sulfon-N-methylanilide 2-cyanoacetylcoumarone-S-(N-v-phenylpropyl)-p-tert.

amylsulfonanilide l-p-laurylphenyl-3-methyl-5-pyrazolone 1-,3-naphthy1-3-amyl-5-pyrazolone l-p-nitrophenyl-B-n-amyl-S-pyrazolone l-p-phenoxyphenyl-3-n-amyl-S-pyrazolone 1-phenyl-3-n-amyl-5-pyrazolone 1,4-phenylene bis-3-( l-phenyl-S-pyrazolone) 1-phenyl-3-acetylamino-5-pyrazolone 1-phenyl-3-propionylamino-5-pyrazolone 1-phenyl-3-n-valerylamino-5pyrazolone 1-phenyl-3-chloroacetylamino-5-pyrazolooe 1-phenyl-3-dichloroacetylarnino-5-pyrazolone 1-phenyl-3-benzoylamino-5-pyrazolone 1-phenyl-3- (m-aminobenzoyl) amino-S-pyrazolone l-phenyl-3-(p-sec. amylbenzoylarnino)-5-pyrazolone 1phenyl-3-diamylbenzoylamino-5-pyrazolone l-phenyl-3-5-naphthoylamino5'-pyrazolone l-phenyl-3-phenylcarbamylamino-5-pyrazolone 1-phenyl-3-palmitylarnino-5 -pyrazolone l-phenyl-3 -benzenesulfonylamino-S-pyrazolone 1- (p-phenoxyphenyl) -3- (p-tert. amyloxybenzoyl) amino- 5-pyrazolone 1- (2,4',6'-tribromophenyl) -3-benzamido-5-pyrazolone l- 2',4,6'-trichlorophenyl) -3-benzamido-5-pyrazolone 1- (2,4,6-trichlorophenyl -3 -phenylacetamido-5-pyrazolone 1-(2,4,6'-tribromophenyl) -3-phenylacetamido-5-pyrazolone l- 2',4'-dichlorophenyl) -3- 3"-(2',4"-di-tert. amylphenoxyacetamido benzamido] -5 -pyrazolone 1-(2,4,6-trichloropheny1) -3- [3 (2"",4-di-tert. amylphenoxyacetamido benzamido] -5-pyrazolone 1- (2,4',6-tribrornophenyl -3- 3"-(2",4"-di-tert. amylphenoxyacetarnido benzamido] -5-pyrazolone 1- (2,4',6-trichlorophenyl) -3- [d (2"',4-di-tert. amylphenoxylpropionamido] -5-pyrazolone 1-( 2',4,6'-tribromophenyl) -3 B-(2,4"-di-tert. amylphenoxy) propionamido] -5-pyrazo1one 1- (2',5 '-dichloro -3- [3 (4-tert. amylphenoxy) benzamido] -5-pyrazolone l-(2,4,6-tribromophenyl) -3-[3"-(4"-tert. amylphenoxy) benzamido] -5-pyrazolone 6 1- 2,S -dichlorophenyl) -3- 3 2"',4-di-tert. amylphenoxyacetamido benzamido] -5-pyrazolone COUPLERS PRODUCING YELLOW IMAGES N-amyl-p-benzoylacetaminobenzene sulfonate N- 4-anisoylacetaminobenzenesulfonyl) -N-benzyl-mtoluidine N- (4-benzoylacetaminobenzenesulfonyl) -N-benzyl-mtoluidine N- (4-benzoylacetaminobenzenesulfonyl) -N-n-amyl-ptoluidine N- (4-b enzoylacetamidobenzenesulfonyl) -N-benzylaniline w- (p-Benzoylbenzoyl) acetanilide w-Benzoylacct-2,5'-dichloroanilide w-Benzoyl-p-sec.amylacetanilide N ,N'-di (w-benzoylacetyl) -p-phenylenediamine N,N'-di-( acetoacetamino diphenyl a-{ 3- oc- 2,4-di-tert.-amylphenoxy) butyramido] benzoyl}- Z-methoxyacetanilide a-{3- u- (2,4-di-tert.-arnylphenoxy) acetamido] benzoy1}-2- methoxyacetanilide 4,4-diacetoacetamino 3,3-dimethyldipheny1 p,p-Diacetoacetamino diphenylmethane Ethyl-p-benzoylacetaminob enzenesulfonate N onyl-p-benzoylacetaminobenzenesulfonate N-phenyl-N- (p-acetoacetaminophenyl) urea n-Propyl-pbenzoylacetaminobenzenesulfonate acetoacetpiperidine w Benzoylacetpiperidide N w-benzoylacetyl) 1 ,2,3 ,4-tetrahydroquinoline N w-b enzoylacetyl) morpholine The color developer compositions of the invention can be suitably used to process a wide variety of color photographic products including both photographic films and papers. The above described emulsions can be coated in the usual manner on any suitable support including cellulose nitrate, cellulose acetate, polyesters, polyvinyl acetal, polyethylene terephathalate, polystyrene and related film-forming resins, as well as, paper, glass, metal and the like.

When photographic color products are processed with the subject developer compositions an increased color density results without a similar increase in color fog. The developer compositions of the invention are particularly useful as color developers for improving cyan D-max./fog ratio in multilayer color films of the reversal color type such as illustrated by the well-known Kodachrome film. In processing such material with the developer compositions of the invention, a maximum dye density is obtained in the exposed regions with a minimum of cyan fog in the unexposed areas. Cyan development in the greenand blue-sensitive layers is diminished in accordance with the invention.

The invention is further illustrated by the following examples of preferred embodiments thereof.

Example 1 A solution of g. (1.0 mole) of triethylene glycol in 250 ml. of benzene was heated to boiling on a steam bath. The heat was then shut oif and 119 g. (1.0 mole) of thionyl chloride was added dropwise at a rate sufficient to keep the benzene solution refluxing. After completion of the addition of the thionyl chloride, the resulting solution was refluxed for about 5 more minutes, after which the volatile constitutents were stripped off with a water aspirator. The remaining syrupy residue was dissolved in ethyl acetate, boiled with charcoal, filtered, and the solvent evaporated in vacuo. The remaining sulfite ester polymer was a light amber syrup having an average molecular weight of about 1540. Similarly, other polymeric compositions of the invention were prepared by substituting other polyalkylene glycols or by employing other proportions of benzene solvent to reactants. The

details of the preparation of several polymeric compositions of the invention are summarized by the data set out in Table A below.

1 Carbowox 200, a polyethylene glycol having an average molecular weight of about 200. In a similar manner polybutylene derivatives can be prepared by substituting a polybutylene glycol such as dibutylene or tributylene glycol for the described alkylene glycols.

Example 2 A color film comprising a cellulose acetate support containing superimposed gelatino-bromoiodide emulsion layers sensitized to red, green and blue with the redsensitive layer next to the support and the blue-sensitive layer furthest from the support was prepared. The bluesensitive and green-sensitive layers were separated by a yellow colloidal silver interlayetr. Reference is made to Mannes et al. US. Patent 2,252,718, issued August 19, 1941, for the details of preparation for such films. The color film was then exposed for second to a 500 watt, 3000" K. light source through a Wratten #29 filter plus a 0.6 neutral density filter On an Eastman Type Ib sensitoi'neter. The exposed film was then developed for 8 minutes at 80 F. in an MQ photographic developer having the formula below:

MQ DEVELOPER Potassium bromide 4.0 Sodium sulfite (anhydrous) 72.0 Hydroquinone 8.8 N-methyl-p-aminophenol sulfate 2.2 Sodium carbonate (anhydrous) 48.0

Water added to make 1 liter.

After the development, the resulting film containing a black-and-white silver negative image was washed in water for 2 minutes, then given a 2 minute antifoggant bath and then washed again in water for 2 minutes, the antifoggant bath having the formula:

ANTIFOGGANT BATH 3 (2 benzothiazolyl methyl) benzothiazolium -ptoluene sulfonate g 0.5 Methanol cc 100 Water cc 900 The resulting film was then given a reversal exposure through the support for 15 seconds through a Wratten #92 filter with a No. 2 Photofiood light set at a distance of one meter. Samples of the resulting film were then developed for 10 and minute intervals in a cyan developer having the formula:

CYAN DEVELOPER 8 CYAN DEVELOPERContinued H-acid --g-.. Water to make 1 liter.

Sodium hydroxide to make pH 10.5.

Sample of film were developed in the described cyan developer containing 0, 0.3, 1.0 and 3.0 grams per liter of developer of the sulfite ester polymer of the invention described in Example 1, Table A, compound 2. The resulting cyan-developed film was then washed for 10 minutes in water, bleached for 2 minutes, fixed for 2 minutes and washed again for 5 minutes, the bleach having the formula:

BLEACH Sodium hexametaphosphate 1.0 Potassium ferricyanide 100 Sodium bromide 34.4 Water to make 1 liter.

and the fix having the formula:

FIX

G. Sodium hexametaphosphate 10.0 Sodium sulfite 10.0 Sodium thiosulfate pentahydirate 320 Water to make 1 liter.

TABLE B 10 Minute Cyan Development 15 Minute Cyan Cone. of the Sulfite Ester Development Polymer in Cyan Developer D-max. Fog D-max. Fog.

Example 3 The color film having the emulsion layers described in Example 2 was exposed in an Eastman Type Ib sensitometer as described in Example 2 and then developed for 3 minutes and 30 seconds at F. in an MQ photographic developer having the formula:

MQ DEVELOPER Sodium hexametaphosphate 1.0 Sodium sulfite 72.0 Hydroquinone 2.0 N-methyl-p-aminophenol sulfate 8.0 Potassium iodide 0.01 Sodium bromide 4.3 Sodium carbonate monohydrate 36.0 Sodium sulfate 15.0 Hydroquinone monosulfonate 1.5 Sodium thiocyanate 1.5

Water added to make 1 liter. Sodium hydroxide added to make pH 10.4.

After development, the resulting film containing a blackand-white silver negative image was washed in water for 2 minutes and then re-exposed through a Wratten #92 filter as described in Example 2. Samples of the resulting film were then developed for 5 and 8 minute intervals in a cyan developer having the following formula and containing various sulfite ester polymeric addenda of the invention:

CYAN DEVELOPER Sodium hexametaphosphate 1.0 Sodium bromide 2.5 Potassium iodide .015

9 CYAN DEVELOPERContinued G. Sodium sulfit 10.0 Sodium sulfate 20.0 Z-amino-S-diethylamino toluene hydrochloride 2.5

6-nitrobenzimidazole nitrate 0.15

Monobenzylaminophenol 0.5 l-hydroxy 2[B(2 acetoamidophenethyl)lnaphthamide 1.5

Water added to make 1 liter. Sodium hydroxide added to make pH 12.5.

The resulting cyan-developed film was then washed for minutes in water, bleached for 3 minutes, fixed for 2 minutes and washed again for 5 minutes, the bleach and fix employed being described in Example 2. Table C below summarizes the color density to fog ratios for cyan development times of 5 and 8 minutes in the cyan developer containing 3 grams per liter of developer of the various sulfite ester polymers described in Table A of Example 1.

1 The polymeric addenda correspond in number to the sulfite ester polymers identified in Table A of Example 1.

Example 4 Samples of a single layer gelatino-bromoiodide emulsion optically sensitized to the green portion of the spectrum and coated on a cellulose acetate support were exposed for ,4 second to a 500 watt, 3000 K. light source through a Wratten No. 61 filter plus a No. 16 filter on an Eastman Type II) sensitometer. The exposed film samples were then developed to form a black-and-white silver negative image as described in Example 2, and washed in water for 3 minutes. One-half of the samples were given a reversal exposure through the support for 10 seconds with a No. 2 Photoflood lamp set at a distance of one meter. The remaining strips were not given this reexposure so that the fog level of the strip could be determined. All of the film samples were then developed for 10, and minute intervals in the cyan developer described in Example 2. Thereafter the cyan-developed film samples were washed, bleached and fixed as described in Example 2. The ratio of maximum densities of the strips which were re-exposed to that of the strips which were not re-eXposed is similar to the D-max/fog ratio of a multilayer coating. Table D below summarizes the color D-max./fog ratios obtained for the various development times, the cyan developer containing one gram per liter of several of the sulfite ester polymeric addenda of the invention as described in Example 1.

The polymeric addenda correspond in number to the snlflte ester polymers identified in Table A of Example 1.

The Wratten filters referred to herein are well-known in the art and are described in Handbook of Chemistry and Physics, 30th Ed. 1947, pages 2269-2279, Chemical Rubber Publishing 00., Cleveland, Ohio. The molecular weights referred to herein were determined by the conventional boiling point elevation method.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. An alkaline aqueous developer composition for color photography comprising: (1) an aromatic primary amine developing agent containing, in addition to the primary amine radical, a substituent selected from the group consisting of hydroxyl radicals and amino radicals, and; (2) .1 to 10 grams per liter of said developer composition of a sulfite ester polymer consisting essentially of the recurring structural unit 0 1 0soX- wherein X is a polyoxyalkylene radical'having alkylene moieties with 2v to 4 carbon atoms and an average molecular weight of less than about 300.

2. A photographic developer composition for color photography comprising an aqueous alkaline solution of an arylene-diamine photographic developing agent and .1 to 10 grams per liter of said developer composition of a sulfite ester polymer having an average molecular weight in the range of about 400 to 3000 and consisting essentially of the recurring structural unit OSOX wherein X is a polyoxyalkylene radical having alkylene moieties with 2 to 4 carbon atoms and an average molecular weight of less than about 300.

3. A photographic developer composition for color photography comprising an aqueous alkaline solution of a p-phenylenediamine color developer, a color-forming compound capable of coupling with the oxidation products of said p-phenylenediamine color developer and .1 to 10 grams per liter of said developer composition of a sulfite ester polymer having an average molecular weight in the range of about 400 to 3000 and consisting essentially of the recurring structural unit 0 T OSOX wherein X is a polyoxyalkylene radical having alkylene moieties with 2 to 4 carbon atoms and an average molecular weight of less than about 300.

4. A photographic developer composition for color photography comprising an aqueous alkaline solution of a p-phenylenediamine color developer, a phenolic cyan coupler compound capable of coupling with the oxidation products of said p-phenylenediamine color developer and .1 to 10 grams per liter of said developer composition of a sulfite ester polymer having an average molecular weight in the range of about 400 to 2000 and consisting essentially of the recurring structural unit wherein X is a polyoxyalkylene radical having alkylene moieties with 2 to 4 carbon atoms and an average molecular weight of less than about 300.

5. A photographic developer composition as described in claim 4 wherein X is a radical having the structure -(CH CH O) 6. A photographic developer composition as described in claim 4 wherein X is a radical having the structure CH CH O 7. A photographic developer composition as described in claim 4 wherein X is a radical having the structure -(CH CH O) 8. A photographic developer composition as described in claim 4 wherein X is a polyoxyethylene radical having an average molecular weight of about 200.

9. A photographic developer composition as described in claim 4 wherein X is a polyoxyethylene radical.

10. A photographic developer composition as described in claim 4 wherein X is a polyoxypropylene radical.

ll. In a photographic reversal color process wherein a multilayer photographic element containing a plurality of differentially sensitized photographic silver halide emulsion layers is given a first exposure, followed by development in a photographic developer for producing a blackand-white negative image and a second exposure, followed by at least one additional development in a photographic developer for producing a colored image, said colored image bearing a complementary relationship to the region of the spectrum to which said photographic silver halide emulsion has been differentially sensitized, the improvement which comprises producing said colored image by developing in an aqueous alkaline color developer composition comprising: (I) an aromatic primary amine developing agent containing, in addition to the primary amine radical, a substituent selected from the group consisting of hydroxyl radicals and amino radicals, and; (2) .1 to 10 grams per liter of said developer composition of a sulfite ester polymer consisting essentially of the recurring structural unit l -OSOX wherein X is a polyoxyalkylene radical having alkylene moieties with 2 to 4 carbon atoms and an average molecular weight of less than about 300.

12. In a photographic reversal color process wherein a multilayer photographic element containing a plurality of differentially sensitized photographic silver halide emulsion layers is given a first exposure, followed by development in a photographic developer for producing a blackand-white negative image and a second exposure, followed by at least one additional development in a photographic developer for producing a colored image, said colored image bearing a complementary relationship to the region of the spectrum to which said photographic silver halide emulsion has been differentially sensitized, the improvement which comprises producing said colored image by developing in an aqueous alkaline color developer composition comprising an arylenediamine photographic developing agent and .1 to 10 grams per liter of said developer composition of a sulfite ester polymer having an average molecular weight in the range of about 400 to 3000 and consisting essentially of the recurring structural unit wherein X is a polyoxyalkylene radical having alkylene moieties with 2 to 4 carbon atoms and an average molecular weight of less than about 300. 1

13. In a photographic reversal color process wherein a multilayer photographic element containing a plurality of diiferentially sensitized photographic silver halide emulsion layers is given a first exposure, followed by development in a photographic developer for producing a blackand-white negative image and a second exposure, followed by at least one additional development in a photographic developer for producing a colored image, said colored image bearing a complementary relationship to the region of the spectrum to which said photographic silver halide emulsion has been diiferentially sensitized, the improvement which comprises producing said colored image by developing in an aqueous alkaline color developer composition comprising a p-phenylenediamine color developer, a color-forming compound capable of coupling with the oxidation products of said p-phenylenediamine color developer and .1 to 10 grams per liter of said developer composition of a sulfite ester polymer having an average molecular weight in the range of about 400 to 3000 and consisting essentially of the recurring structural unit wherein X is a polyoxyalkylene radical having alkylene moieties with 2 to 4 carbon atoms and an average molecular weight of less than about 300.

14. In a photographic reversal color process wherein a multilayer photographic element containing a plurality of differentially sensitized photographic silver halide emulsion layers is given a first exposure, followed by development in a photographic developer for producing a black-and-white negative image and a second exposure, followed by at least one additional development in a photographic developer for producing a colored image, said colored image bearing a complementary relationship to the region of the spectrum to which said photographic silver halide emulsion has been differentially sensitized, the improvement which comprises producing said colored image bydeveloping in an aqueous alkaline color developer composition comprising an alkali metal sulfite, a p-phenylenediamine color developer, a phenolic cyan coupler compound capable of coupling with the oxidation products of said p-phenylenediamine color developer and .1 to 10 grams per liter of said developer composition of a sulfite ester polymer having an average molecular weight in the range of about 400 to 2000 and consisting essentially of the recurring structural unit wherein X is a polyoxyalkylene radical having alkylene moieties with 2 to 4 carbon atoms and an average molecular weight of less than about 300.

15. A photographic reversal color process as described in claim 14 wherein X is a radical having the structure (CH CH O) 16. A photographic reversal color process as described in claim 14 wherein X is a radical having the structure (CH CII O) 17. A photographic reversal color process as described in claim 14 wherein X is a radical having the structure -(CH CH O) 18. A photographic reversal color process as described in claim 14 wherein X is a polyoxyethylene radical having an average molecular weight of about 200.

19. A photographic reversal color process as described in claim 14 wherein X is a polyoxyethylene radical.

20. A photographic reversal color process as described in claim 14 wherein X is a polyoxypropylene radical.

No references cited.

Claims

12. IN A PHOTOGRAPHIC REVERSAL COLOR PROCESS WHEREIN A MULTILAYER PHOTOGRAPHIC ELEMENT CONTAINING A PLURALITY OF DIFFERENTIALLY SENSITIZED PHOTOGRAPHIC SILVER HALIDE EMULSION LAYERS IS GIVEN A FIRST EXPOSURE, FOLLOWED BY DEVELOPMENT IN A PHOTOGRAPHIC DEVELOPER FOR PRODUCING A BLACKAND-WHITE NEGATIVE IMAGE AND A SECOND EXPOSURE, FOLLOWED BY AT LEAST ONE ADDITIONAL DEVELOPEMENT IN A PHOTOGRAPHIC DEVELOPER FOR PRODUCING A COLORED IMAGE, SAID COLORED IMAGE BEARING A COMPLEMENTARY RELATIONSHIPO TO THE REGION OF THE SPECTRUM TO WHICH SAID PHOTOGRAPHIC SILVER HALIDE EMULSION HAS BEEN DIFFERENTIALLY SENSITIZED, THE IMPROVEMENT WHICH COMPRISES PRODUCING SAID COLORED IMAGE BY DEVELOPING IN AN AQUEOUS ALKALINE COLOR DEVELOPER COMPOSITION COMPRISING AN ARYLENEDIAMINE PHOTOGRAPHIC DEVELOPING AGENT AND 1 TO 10 GRAMS PER LITER OF SAID DEVELOPER COMPOSITION OF A SULFITE ESTER POLYMER HAVING AN AVERAGE MOLECULAR WEIGHT IN THE RANGE OF ABOUT 400 TO 3000 AND CONSISTING ESSENTIALLY OF THE RECURRING STRUCTURAL UNIT