US3135605A - Novel photographic products, processes, and compositions employing novel anthraquinone dye developers - Google Patents

Description

United States Patent Office dddhddd Patented June 2, 1%64 Delaware No Drawing. Filed Feb. 15, 1962, Ser. No. 173,357 28 Claims. (Cl. 96-2?) This invention relates to photography and more particularly to products, compositions and processes for the development of photosensitive silver halide elements.

It is one object of the present invention to provide novel processes and compositions for the development of silver halide emulsions, in which novel colored silver halide developing agents are used.

Another object is to provide novel processes and compositions for the development of silver halide emulsions, in which the novel silver halide developing agent is capable of developing an exposed silver halide emulsion and imparting a reversed or positive colored image of the developed image to a superposed image-receiving material.

Further objects are to provide said novel silver halide developing agents, and novel products, processes and compositions suitable for use in preparing monochromatic and multichrornatic photographic images by the employment of said novel silver halide developing agents.

(Ether objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the products and compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims. 7

The objects of this invention may be accomplished by the use of certain novel dyes which have the ability to develop an exposed silver halide emulsion; thus these dyes may be referred to as dye developers. These novel dyes or dye developers Will be further described hereinafter.

The dye developers and the photographic processes and compositions disclosed herein are particularly useful in the treatment of an exposed silver halide emulsion, whereby a positive dye image may be imparted to another element, herein referred to as an image-carrying or image-receiving element.

US. Patent No. 2,983,606, issued May 9, 1961, to Howard G. Rogers, discloses diiiusion transfer processes wherein a photographic negative material, such as a photographic element comprising an exposed silver halide emulsion, is developed in the presence of a dye developer to impart to an image-receiving layer a reversed or positive dye image of the developed image by permeating into said emulsion a suitable liquid processing composition and bringing said emulsion into superposed relationship with an appropriate image-receiving layer. The inventive concepts herein set forth provide novel dye developers which may be advantageously used in such processes.

In carrying out the process of this invention, a photosensitive element containing a silver halide emulsion is exposed and Wetted with a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in the dark, and the photosensitive element superposed prior to, during or after wetting, on an imagereceiving element. In a preferred embodiment, the photosensitive element contains a layer of dye developer, and

the liquid processing composition is applied to the photosensitive element in a uniform layer-as the photosensitive element is brought into superposed position with an image-receiving element. The liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby providing an image-wise distribution of unoxidized dye developer dissolved in the liquid processing composition. This immobilization is apparently due, at least in part, to a change in the solubility characteristics of the dye developer upon oxidation, and especially as regards its solubility in alkaline solutions. It may also be due, in part, to a tanning effect on the emulsion by the oxidized developing agent. At least part of this image-wise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed in1age-receiving layer. The image-receiving layer receives a depth-Wise diffusion, from the emulsion, of unoxidized dye developer, Without ap preciably disturbing the image-wise distribution thereof, to provide a reversed or positive, colored image of the developed or negative image. The image-receiving element may contain agents adapted to mordant or otherwise fix the diilused, unoxidized dye developer. Imbibition periods of approximately one minute have been found to give good results, but this contact period may be adjusted where necessary to compensate for variations in temperature or other conditions. The desired positive image is revealed by separating the image-receiving layer from the silver halide emulsion at the end of the imbibition period.

The dye developers of this invention may be utilized in the photosensitive element, for example, in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element or in the liquid processing composition. In a preferred embodiment, a coating or layer of the dye developer is placed behind the silver halide emulsion, i.e., on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the image-receiving layer when in superposed relationship therewith. Placing the dye developer behind the emulsion layer, as in the preferred embodiment, has the advantage of providing increased contrast in the positive image, and also minimizes any light-filtering action by the colored dye developer. In this preferred embodiment, the layer of dye developer may be applied by using a coating solution containing, e.g., about 0.5 to 8%, by weight, of the dye developer. Similar concentrations may be used if the dye developer is utilized as a component of the liquid processing composition. In an especially useful mode of disposing the dye developers in the photosensitive elements, the dye developer is dissolved in a Water-immiscible solvent and then dispersed in a gelatin coating solution.

The liquid processing composition which is used in the processes herein disclosed comprises at least an aqueous solution of an alkaline compound, for example, dietnylamine, sodium hydroxide or sodium carbonate, and may containthe dye developer. In some instances, it may contain an additional silver halide developing agent. If the liquid processing composition is to be applied to the emulsion by being spread thereon, preferably in a relatively thin, uniform layer, it may also include a viscosity-increasing compound constituting film-forming material of the type which, when spread over a water-absorbent base, will form a relatively firm and relatively stable film. A preferred film-iorming material is a high molecular Weight polymer such as a polymeric, watera 4 soluble ether inert to an alkali solution, as, for example, (2) a hydroxyethyl cellulose or sodium carboxymethyl cellu- OH lose. Other film-forming materials or thickening agents CH3 whose ability to increase viscosity is substantially unaf- (I? NII-HGHNIIG fected when left in solution for a long period of time 5 may also be used.

Application Serial No. 173,356, filed concurrently here- I with in the name of Milton Green, discloses and claims a on class of dye developers which are particularly useful in I! photographic products, processes and compositions such C1I3-CHZCHNH O as described above. oI-noI-r The present invention relates to a subgeneric group 1 [a methy1 B (3 [2" 5"-dihydroxyphenyll.benzamido).profalling Within the scope Of the broad class Of compounds pylamino]-5'a-hydroxymethylpropylamino anthraquinonc OH on i ii I CNHOH-OH-NH 0 I OH described in the aforementioned copending application L -l y -fi-(3[ ,5"-dil1ydroxyp11cny1]-benzamido)- of Milton Green. The compounds of the present invenpl'opylammol'flnthmquinone tion are magenta dye developers which exhibit excellent CH CH 0 OH spectral absorption characteristics and which possess par- I 3 3 II ticularly good light stability. The compounds of the -Nfi-C- present invention are therefore especially useful in difiusion transfer processes for obtaining monochromatic or multicolor images. These compounds may be represented I by the following formula: OK (A) OH -NH 0 II I 40 1-[a-methyl-B-(3- [2",5-dihydroxyp11enyl] -benzamido)- propylamino] -5-ani1ino anthraquinone on CI a I a (I? l l IIIIICHCHN1I-C H H3O i i wherein R is lower alkylene preferably containing not I more than three carbon atoms; R may be lower alkylene, 011 including alicyclic; or arylene such as phenylene; Ar is I I phenylene or a lower alkyl derivative thereof, e.g., tolyl- CH3CHNH O ene; and Y may be hydrogen, hydroxyl, or

OH l-[a-methyl-B-(2'metl1yl-5-[2,5-dil1ydroxypheny1]-benz- O 5 amido)-propylamin0]-5-is0propylamino anthraquinonc 6 H N-CAr 3 OH; (I) (I) I (II) NII-CH-JJH-NIL-(J- OH i i As illustrations of useful compounds within the scope of Formula (A), mention may be made of the following I magenta dye developers: 0H 0H CHNH 0H CH3 CH 0 5 CH ll (I? H-oHoH-NH-o 0H; 0H

1-[a-metl1y1-fl-(3[2,5"-dil1ydroxypl1enyl]-beuzamido) propylamino]-5-(a-methyl-B-hydroxypropylamino) anthraqui- I none In addition to the aforementioned examples and fur- 1 l ther as illustrative of compounds within the scope of this invention, CHQOH I 1- a-methyl-B- (3- [2 ,5 "-dihydroxyphenyl] -benza1nido) Y-R-N propylamino]-5-is0pr0py1amiu0 anthraquinone of Formula A may comprise other alkylamino substituents such as t-butylamino, an alicyclic amino such as cyclohexylamino, an amino sugar such as d-glucoamino, an aromatic amino such as m-anisidino, etc.

The novel anthraquinone dye developers of this invention may be prepared by reacting together in the presence of a suitable hydrogen acid acceptor such as, for example, quinoline, anhydrous pyridine, etc., a compound of the formula:

wherein Ar has the meaning heretofore given and D is a protected hydroquinonyi developing function, that is, a hydroquinonyl radical wherein the hydroxy groups have been modified so that they will not take part in the reaction but may be converted to form the hydroquinonyl radical by subsequent chemical treatment such as hydrolysis, e.g., 2,5-bis-acyloxyphenyl group; and an anthraquinone dye of the formula:

wherein R and R have the meanings heretofore given and Y may be hydrogen, hydroxyl, or a primary amino group. After reaction, and prior to use as a photographic dye developer, the protected groups of D, e.g., the acyloxy groups are removed by chemical treatment such as hydrolysis to form the hydroquinonyl developing function.

The following examples show by way of illustration and not by way of limitation the synthesis of the novel anthraquinone dye developers of this invention.

EXAMPLE 1 1- [a-Methyl-B- (3- [2,5-Dihydroxyphenyl] -Benzamido) -Prpylamin0] -5-Is0pr0pylamino A nihraquinone 2.0 g. of 1-[fl-amino-u-methyl-propylamino-S-isopropylamino anthraquinone were dissolved in 50 ml. of pyridine. 2.0 g. of solid 3-diacetoxyhydroquinonyl benzoyl chloride were added and the resulting mixture was then heated and stirred at just below the refiux temperature for one hour. It was then poured into a dilute HCl/ ice mixture and a solid material was precipitated out. This precipitated solid was then filtered, washed with dilute HCl, then washed with water and dried. It was then dissolved in 50 ml. of methyl Cellosolve and the resulting solution was deaerated by bubbling nitrogen through it for minutes. Similarly, a solution of 6.0 g. of sodium hydroxide in 500 ml. or" water was deaerated by bubbling nitrogen through it for 15 minutes. The methyl Cellosolve solution was then added to the sodium hydroxide solution under a blanket of nitrogen, and the mixture was stirred at room temperature for one hour to etiect complete solution. The solution was then filtered and carbon dioxide gas was bubbled in until a pH of 7-8 was obtained. A magenta powder precipitated and was filtered, washed thoroughly with Water and dried in a desiccator to yield 2.7 g. of a magenta dye developer, l-[a-methyl- [5' (3 [2,5"-dihydroxyphenyl] -benzamido)-propylamino]-S-isopropylamino-anthraquinone, having the follow- 7 ing structural formula:

It had a melting point of 144-7 (3., exhibited a spectral absorption curve which showed a A at 522 my. in methyl Cellosolve; e=l2,400. It was soluble in methyl Cellosolve, dimethyl formamide and aqueous sodium hydroxide, and sparingly soluble in ethyl alcohol and acetone.

Analysis:

Calculated 72. 45 5. 7. 46 Found 72.21 6.14 7. 80

EXAMPLE 2.

J- [u-Meihyl-B- (3'- [2",5"-Dihydroxyphenyl] -Benzamido) -Pr0pylamino] -5-u-Hydroxymethylpropylamino A n thraquinone 2.0 g. of l-[fl-amino-a-methyl-pyropylamino]-5-a-hydroxymethylpropylamino anthraquinone were dissolved in 50 ml. of pyridine. 3.0 g. of 3-diacetoxyhydroquinonyl benzoyl chloride were added and the mixture was then heated at C. for 35 minutes, after which it was poured into an excess of dilute HCl/ice to precipitate a magenta solid. This solid was filtered, washed with dilute HCl, then with water and dried. It was then dissolved in methyl Cellosolve, deaerated, hydrolyzed with a deaerated sodium hydroxide solution, filtered and treated with carbon dioxide gas, all as in Example 1, to precipitate a magenta powder. This powder was filtered, Washed with water and dried to yield a magenta dye developer, l-(a-methyl- B (3'- [2",5"-dihydroxyphenyl]-benzamido)-propylamino]-5-a-hydroxymethylpropylamino anthraquinone, having the following structural formula:

OH CH CH3 1 p NH-oH-oH NH-o0 I OI-I l u CH-NH o It had a melting point of l26-l3 1 C., exhibited a spectral absorption curve which showed a A at 525 mg in methyl Cellosolve; e=13,600. It was soluble in methyl Cellosolve, dimethyl formamide and aqueous sodium hydroxide, and sparingly soluble in ethyl alcohol.

EXAMPLE 3 5.0 g. of 1,5 -bis- (B-amino-u-methyl-propylamino) anthraquinone were dissolved in ml. of pyridine. 15 g. of B-diacetoxyhydroquinonyl benzoyl chloride were added and the solution was stirred at 100 C. for 90 minutes, then cooled and poured into an excess of dilute hydrochloric acid/ice mixture. A magenta solid was precipitated out. This solid was filtered, washed with dilute acid, then with water and dried. It was then dissolved in 50 ml. of methyl Cellosolve, deaerated, and

7 8 added slowly to an oxygen-free solution of 10 g. of sodi- (3'-[2",5"-dihydroxyphenyl] benzamido) propylamium hydroxide in 500 ml. of water as in the foregoing examno]--isopropylamino anthraquinone dissolved in cc. ples. The mixture Was stirred at room temperature for of 2% cellulose acetate hydrogen phthalate in a 50:50 one hour to effect complete solution. Carbon dioxide mixture, by volume, of acetone and tetrahydrofuran. gas was then bubbled in until a pH of 7-8 was obtained. 5 After this coating dried, a green-sensitive silver iodobro- A magenta solid was precipitated and was filtered, washed mide emulsion was coated on at a speed of 5 feet/minwith water and dried to yield 2.0 g. of a magenta dye deute and allowed to dry. This photosensitive element was veloper, 1,5 bis-[cr-methyI-B-(B'-[2,5"-dihydroxyphenexposed, and processed by spreading between the thus yl]-benzamido)propylamino]-anthraquinone. exposed photosensitive element and a superposed imageom CH3 OH OH OH I ll I ll NH-oH0H NH 0 CH3 OH:

| OH It had a melting point of 116-121" C., exhibited a spectral receiving element, an aqueous processing composition absorption curve which showed a )t at 522 my in methyl 2r comprising: Cellosolve; e=12,600. It was soluble in ethyl alcohol, a Water 100 methyl Cellosolve, dimethyl formamide, acetone and aque- NaOH 5 Sodlum hydroxlde- Hydroxyethyl cellulose (high viscosity) [commer- PL 4 cially available from Hercules Powder Co., under tl t d m fN trosol 250 4.03 I-[a-Methyl-fi-(B [2",5"-Dihydroxyphenyl]-Benzami- 3O z z g g i i i 23 d0)-Propylamino]-5-Anilino-Anthraquinone Sodium thiosuifate 1.15 700 mg. of l-(fi-amino-oc-methyl-propylamino)-5-ani- N-bcnzyl-oc-picolinium bromide g 2.3 lino anthraquinone were dissolved in ml. of pyradine. Th image-receiving element comprised a 2;1 i t gof 3diacetmyhydfoquinonyl benzoyl chloride Were by weight, of polyvinyl alcohol and poly-4-vinylpyridine added and the mixture W215 heated t0 100 C. for minon a bayyta paper support, After an imbibition period Utes, l Cooled and PQ into EXCESS dihlte of approximately one minute, the image-receiving element Hcl/ A magenta Solid was preclpltated- T1115 S011d was separated and contained a magenta positive image.

was filtered, washed with dilute acid, then with water and dried. It was then dissolved in 25 ml. of methyl 4 X P 6 Cellosolve and hydrolyzed with sodium hydroxide solu- The Procedure descflbed pl 5 repeated, tion under a blanket of nitrogen, as in the foregoing exexcept h the dye dfweloper W dlspefsfll 111 a layer amples. The alkali solution was then filtered and carof 8 The coating 501110011 from WhIFh the y bon dixoide gas bubbled in until a pH of 78 was obdeveloper was mated P p y addlng tained. A magenta solid precipitated and Was washed of the dye developer dlSSOlVed 1n 1 cc. of cyclohexanone with water and dried to yield a magenta dye developer, 45 and 5 9 y 'y p Th1s 1111K- 1 p mgz 2" 5" benzami ture was agitated in a Waring Blendor for two minutes do)-propylamino]-5-anilino anthraquinone, having the Wlth a solutlon of 5 of 10% gelatin Solutlon, f following t u t l f l of water, and 1 cc. of Alkanol B. 5 cc. of the resulting OH dye dispersion was added to 10 cc. of water containing 0H, CH3 0 small amounts of saponin and succinaldehyde, and then 0 l coated on the gelatin subcoated cellulose acetate film base II I at a speed of 10 feet/minute.

Substitution of the other dye developers described above in the procedures described in Examples 5 and 6 E gave similar positive transfer images. As was indicated previously, the compounds of the II present invention have been found to possess light stability considerably superior to analogous anthraquinone dye developers such as those disclosed in the aforemen- 0 tioned copending application of Milton Green, Serial No. l-[a-methyl-fl-(3[2",5"-dihydroxyph idM 173,356. This increased stability to light is believed to propylamlno1-5-anilino anthraquinone be due to the presence of the tic-methyl substituent, e.g.,

the It had a melting point of 105-116 0, exhibited a spec- CH3 tral absorption curve which showed a A at 530 m in 5 H,- methyl Cellosolve; e=13,600. It was soluble in aqueous radical in the organic linking radical separating the hysodium hydroxide, methyl Cellosolve and acetone. droquinonyl developing function from the anthraquinone The following examples show by way of illustration and nucleus. Tests conducted by exposing positive images not by way of limitation the photographic utility of the containing the novel dye developers of this invention to a novel compounds of this invention. xenon arc light for a long period of time, e.g., 20 hours, and comparing the results with a control positive ima e EICAMPLE 5 not so exposed, show appreciably less loss of density up n A photosensitive element was prepared by coating a exposure to light, thereby demonstrating the improved gelatin subcoated film base at a speed of 5 feet/minute stability to light of positive images prepared in the manwith a solution comprising 0.43 g. of l-[ot-methyl-pner of this invention. Since the advantages of obtain- 2 ing photographic prints which will not fade significantly with the passage of time are apparent, the usefulness of the photogarphic products, processes and compositions of this invention will likewise be apparent.

The dye developers of thisinvention are also useful in integral multilayer photosensitive elements for use in multicolor difiusion transfer processes. As an example of such photosensitive elements, mention may be made of the photosensiti'e elements disclosed and claimed in the copending US. application of'Edwin H. Land and Howard G. Rogers, Serial No. 565,135, filed February 13, 1956, wherein at least two selectively sensitized photo sensitive strata are superposed on a single support and are processed, simultaneously and without separation, with a single common image-receiving element. A suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a bluesensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer. and a yellow dye developer. In one of the preferred embodiments of photosensitive elements of this type, the dye developers are disposed in separate alkali-permeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.

The photosensitive elements within the scope of this invention may be used in roll film units which contain a plurality of photosensitive frames. The photosensitive elements of this invention are especially useful in composite roll film intended for use in a Polaroid Land Camera, sold by Polaroid Corporation, Cambridge 39,

Massachusetts, or a similar camera structure such, for

example, as the camera forming the subject matter of US. latent No. 2,435,717, issued to Edwin H. Land on February 10, 1948. In general, such composite roll films comprise a photosensitive roll, a roll of image-receiving material and a plurality of pods containing an aqueous alkaline processing solution. The rolls and pods are so associated with each other that, upon processing, the photosensitive element may be superposed on the imagereceiving element and the pods may be ruptured to spread the aqueous alkaline processing solution between the superposed elements. The nature and construction of the pods used in such units are well known to the art. See, for example, U.S. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin H. Land.

It will be noted that the liquid processing composition may contain one or more auxiliary or accelerating silver halide developing agents, such as p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol); benzlylaminophenol; hydroquinone; a substituted hydroquinone such as toluhydroquinone, phenylhydroquinone, or 4'-methylphenylhydroquinone; or a 3-pyrazolidone such as 1- phenyl-3-pyrazolidone. These silver halide developing agents are substantially colorless, at least in their unoxidized form. It is possible that some of the dye developer oxidized in exposed areas may be oxidized by an energy transfer reaction with oxidized auxiliary developing agent.

In addition, development may be effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed and claimed in the copending application of Milton Green and Howard G. Rogers, Serial No. 50,851, filed August 22, 1960.

The dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional photosensitive films, plates or papers to obtain black and white, monochromatic or toned prints or negatives. By way of example, a developer composition suitable for such use may comprise an aqueous solution of approximately 1-2% of the dye developer, 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide. After development is completed, any unreacted dye developer is washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble. The expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye, whereas monochromatic is intended to designate dye images free of silver.

It should be noted that the dye developers of this medium are self-sutficientto provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which the color is produced by a coupling reaction between a color former or coupler and the oxidized developing agent, as well as so-called auto-coupling processes in which color is obtained by a reaction of the oxidized developing agent with unoxidized developing agent.

It will be apparent that, by appropriate selection of the image-receiving element from among suitable known opaque and transparent materials, it is possible to obtain either a colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of imagereceiving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of such photographic materials are disclosed in US. Patent No. 2,647,049 to Edwin H. Land.

As examples of useful image-receiving materials, mention may be made of nylon, e.g., N-methoxyrnethyl-polyhexamethylene adipamide, polyvinyl alcohol, and gelatin, particularly polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine. The image-receiving element also may contain a development restrainer, e.g., 1-phenyl-S-mercaptotetrazole, as disclosed in the copending application of Howard G. Rogers and Harriet W. Lutes, Serial No. 50,849, filed August 22, .1960.

The dye developers herein set forth are also useful in the formation of colored images in accordance with the photographic products and processes described and claimed in US. Patent No. 2,968,554, issued to Edwin H. Land on January 17, 1961.

The novel compounds herein disclosed are also suitable for use as dyes for textile fibres, such as nylon. v

In the preceding portions of the specification the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black.

Since certain changes may be made in the above products, compositions and processes without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

l. A photographic developer composition comprising an aqueous alkaline solution containing at least one accelerating silver halide developing agent which is substantially colorless in its unoxidized form and a magenta dye of the formula:

OH H CH H O 11 wherein R is lower alkylene; R is selected from the group consisting of lower alkylene and arylene radicals; Ar is a phenylene radical; and Y is a member of the group consisting of hydrogen, hydroxyl, and

I OH

2. A photographic developer composition as defined in claim 1 wherein said magenta dye is l-[u-methyl-[i-(3- [2",5 dihydroxyphenyl]-benZamido)-propylamino]-5- isopropylamino anthraquinone.

3. A photographic developer composition as defined in claim 1 wherein said magenta dye is l-[oc-methyl-fl-(y- [2",5" dihydroxyphenyl]-benzamido)-propylamino]-5- u-hydroxymethylpropylamino anthraquinone.

4. A photographic developer composition as defined in claim 1 wherein said magenta dye is 1,5-bis-[a-methyl- ;8-(3'-[2,5"-dihydroxypl1enyl]-benzamido) propylamino]-anthraquinone.

5. A photographic developer composition as defined in claim 1 wherein said magenta dye is 1-[ot-methyl-fi-(3'- [2",5-dihydroxyphenyl]-benzamido) propylamino]-5- anilino anthraquinone.

6. A photographic developer composition as defined in claim 1 wherein said magenta dye is 1-[a-methyl-fi-(3'- [2,5-dihydroxyphenyl]-benzamido) propylaminoJ-S- (a-methyl-[i-hydroxypropylamino -anthraquinone.

7. A process of developing an exposed silver halide emulsion which comprises contacting said exposed emulsion with an aqueous alkaline solution containing a magenta dye of the formula:

wherein R is lower alkylene; R is selected from the group consisting of lower alkylene and arylene radicals; Ar is a phenylene radical; and Y is a member of the group consisting of hydrogen, hydroxyl, and

8. The process as defined in claim 7 wherein said dye is disposed, prior to exposure, in a photosensitive element comprising said exposed silver halide emulsion, and the solution containing said dye is formed by permeating said photosensitive element with an aqueous alkaline solution capable of solubilizing said dye.

9. The process as defined in claim 7 wherein said aqueous alkaline solution contains at least one accelerating silver halide developing agent.

10. In a process of forming photographic images in color, the steps which comprise developing an exposed ii 444 silver halide emulsion with an aqueous alkaline solution containing a magenta dye of the formula:

wherein R is lower alkylene; R is selected from the group consisting of lower alkylene and arylene radicals; Ar is a phenylene radical; and Y is a member of the group consisting of hydrogen, hydroxyl, and

thereby to provide in said emulsion a predetermined distribution of unoxidized dye, and transferring at least part of said distribution of unoxidized dye, by imbibition, from said emulsion to an image-receiving layer in superposed relationship with said emulsion to impart to said imagereceiving layer a positive dye image.

11. The process as defined in claim 10 wherein said magenta dye is disposed, prior to exposure, in a photosensitive element comprising said exposed silver halide emulsion, and the solution containing said magenta dye is formed by permeating said photosensitive element with an aqueous alkaline solution capable of solubilizing said magenta dye.

12. The process as defined in claim 11, wherein said solution is introduced by being spread in a substantially uniform layer between said photosensitive element and an image-receiving element including said image-receiving layer as said elements are brought into superposed relationship.

13. The process as defined in claim 12 wherein said solution contains a thickener for increasing viscosity and for facilitating the spreading thereof between said elements.

14. The process as defined in claim 10 wherein said magenta dye is dissolved in an aqueous alkaline solution prior to application thereof to said exposed emulsion.

15. The process as defined in claim 10 wherein said aqueous alkaline solution contains at least one accelerating silver halide developing agent.

16. A photographic process as defined in claim 10 wherein said dye is 1-[oe-methyl-fl-(3-[2,5-dihydroxyphenyl]-benzamido)-propylamino] 5 isopropylamino anthraquinone.

17. A photographic process as defined in claim 10 wherein said dye is l-[a-methyl-fl-(3'-[2",5"-dihydroxyphenyl]-benzamido)-propylamino] 5 a hydroxymethylpropylamino anthraquinone.

18. A photographic process as defined in claim 10 wherein said dye is 1,5-bis-[u-methyl-fi-(3'-[2",5"-dihydroxyphenylJ-benzamido)-propylamino] anthraquinone.

19. A photographic process as defined in claim 10 wherein said dye is 1-[a-methyl-[i-(3'-[2",5"-dihydroxyphenyl] -benzamido)-propylamino 5 anilino anthraquinone.

20. A photographic process as defined in claim 10 wherein said dye is l-[a-methyl-fl-(3'-[2",S"-dihydroxyphenyl]-benzamido)-propylamino] 5 (a-methyl-fl-hydroxy-propylamino)-anthraquinone.

21. A photographic product comprising a support, a silver halide emulsion located in a layer on said support,

wherein R is lower alkylene; R is selected from the group consisting of lower alkylene and arylene radicals; Ar is a phenylene radical; and Y is a member of the group consisting of hydrogen, hydroxyl, and

22. A photographic product as defined in claim 21 wherein said silver halide emulsion and said magenta dye are located in the same layer.

23. A photographic product as defined in claim 21 wherein said silver halide emulsion and said magenta dye are located in adjacent layers.

24. The photographic product as defined in claim 21 wherein said dye is l-[a-methyl-fi-(3-[2",5"-dihydroxyphenyl]-benzamido)-propylamino] 5 isopropylamino anthraquinone.

25. The photographic product as defined in claim 21 wherein said dye is 1-[a-methyl-lfi-(3'-[2",5"-dihydroxyphenyl] -benzamido) -propylamino] 5 0c hydroxymethylpropylamino anthraquinone.

26. The photographic product as defined in claim 21 wherein said dye is 1,5-bis-[u-methyl-B-(3'-[2",5-dihydroxyphenyl] -benzamido) -propylamino] -anthraquinone.

27. The photographic product as defined in claim 21 wherein said dye is 1-[wmflhyl-B-(If-[2,5"-dihydroxyphenyl]-benzamido) propylaminoJ-S-anilino anthraquinone.

28. The photographic product as defined in claim 21 wherein said dye is 1-[a-methyl-B-(3-[2,5"-dihydroxyphenyl]-benzamido)-propylamino] 5 (a-methyl-B-hydroxy-propylamino) -anthraquinone.

References Cited in the file of this patent UNITED STATES PATENTS 2,983,606 Rogers May 9, 1961 FOREIGN PATENTS 804,973 Great Britain Nov. 26, 1958 804,974 Great Britain Nov. 26, 1958 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, $135,605 a I 7 June 2, 1964 Arthur D. Jarrett It is hereby certified that error appears in the above numbered patent requiring correction and that-: the said Letters Patent should read as corrected below.

Column 3, lines 64 to 72, for the lower left-hand portion of the formula reading CH CH-NH H OH CH CHNH column 5 line '52 for "propylamino-"' read propylamimfl 1 column 6 line 31, for "-pyropylamino] read propylamino] column I line 9 for "-benzamido)propylaminoj read -benzamido) -propylamino] line 34,. for "pyradine" read pyridine line 4L3 for "dixoide" read dioxide column 9 lines 12' and l3 for photo sensitive" read photosensitive column 12, line 68, for "propyla mino read -==propylamino] e Signed and sealed this lst day of December 1964;

SEAL Attes-t:

ERNEST W SWIDER I EDWARD J BRENNER Attesting Officer Commissioner of Patents

Claims (1)

10. IN A PROCESS OF FORMING PHOTOGRAPHIC IMAGES IN COLOR, THE STEPS WHICH COMPRISE DEVELOPING AN EXPOSED SILVER HALIDE EMULSION WITH AN AQUEOUS ALKALINE SOLUTION CONTAINING A MAGENTA DYE OF THE FORMULA: