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Publication numberUS3364022 A
Publication typeGrant
Publication date16 Jan 1968
Filing date1 Dec 1966
Priority date1 Apr 1963
Publication numberUS 3364022 A, US 3364022A, US-A-3364022, US3364022 A, US3364022A
InventorsCharles R Barr
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Direct positive photographic color reproduction process and element utilizing thio-substituted hydroquinones as development inhibitors
US 3364022 A
Abstract  available in
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Description  (OCR text may contain errors)

Jan. 16, 1968 c. R. BARR 3,354,022

DIRECT POSITIVE PHOTOGRAIHIC COLOR REPRODUCTION PROCESS AND ELEMENT UTILIZING THIO-SUBSTITUTED HYDROQUINONES AS- DEVELOPMENT INHIBITORS Filed Dec. 1, 1966 DEVELOPMENT INHIBIT OR LRELEASING COMPOUND, A 9X BL: SENSITIVE EMULSION NUCLEATED METAL SALT+ YELLOW-FORMING COUPLER BARR/ER LAYER DEVELOPMENT INHIBITOR RELEASING COMPOUND, AgX 6R SENSITIVE EMULSION NUCLEATED METAL SALT+MAOENTA-FORMIN6 COUPLER BARRIER LAYER I DEVELOPMENT INHIBITOR RELEAS/NG COMPOUND, AgX RED SENSITIVE EMULSION NUCLEATED METAL SALTI-CYAN FORMING COUPLER SUPPORT a a PROTECTIVE LA YER 29 051 51. OPMENT/NHIB/TORRELEASING COMPOUND, Agx BL.- 28 SENSITIVE EMULSION A FOGGED Agx raww- FORM/N6 COUPLER 27 BA RIP/El? LA YER 26 DEVELOPMENT INHIBITOR REL EA SING COMPOUND, AgX/PED 25 sgn/s/r/vg EMULSION FOGOED Ag CHIN-FORMING COUPLER BARRIER LAYER DEVEL OPMENT INHIBITOR RE LEASING COMPOUND, AQX 6R SENSITIVE EMULSION FOGGED AyX -I- MAGENTA FORMIN6 COUPLER SUPPORT CHARLES Ii. BARR INVENTOR 2 L ATTORNEYS United States Patent 3,364,622 DIRECT POSITIVEPHOTOGRAPHIC COLOR RE- PRODUCTION PROCESS AND ELEMENT UTI- LIZING THlO-SUBSTITUTED HYDROQUINONES AS DEVELOPMENT INHIBITORS Charles R. Barr, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Continuation-impart of application Ser. No. 412,591, Nov. 16, 1964, which is a continuation-in-part of application Ser. No. 269,346, Apr. 1, 1963. This application Dec. 1, 1966, Ser. No. 598,480

25 Claims. (Cl. 96-3) ABSTRACT OF THE DISCLOSURE Photographic direct positive color elements and processes feature a non-diflusible thio-substituted hydroquinone which reacts with oxidized developing agent to form a diffusible mercaptan development inhibitor. This mercaptan diffuses to a predetermined layer of the photographic element and selectively inhibits development of color former present therein.

This application is a continuation-impart application of our copending application U.S. Ser. No. 412,591, filed Nov. 16, 1964, now abandoned; which is a continuationin-part application of our US. application Ser. No. 269,- 346; filed Apr. 1, 1963, now abandoned.

This invention relates to color photography, and more particularly to photographic direct positive color processes and photographic elements suitable for use in such processes.

Direct positive photographic color processes are well known in the art and generally comprise a number of steps. A typical color process comprises such steps as a black-and-white development to form a negative image, a reversal exposure, development with an aromatic primary amino color developing agent to form insoluble image dyes in the areas of development, and a bleach step to remove developed silver. Color processes are also known whereby color images are transferred to receiving elements and which have the advantage of producing color images free of residual color couplers and other products of development. However, many of such processes of both types involve several complex steps and require several processing baths with large volumes of processing solutions.

It is an object of the present invention to provide a new color process in the photographic art.

It is another object of this invention to provide a new photographic process for producing sharp color images.

It is a further object of this invention to provide a novel photographic diffusion transfer process wherein a dye image is transferred to a receiving layer.

It is another object of this invention to provide a novel color diffusion transfer process that can be effected in one wet processing step.

It is an additional object of this invention to provide a novel color diffusion transfer process wherein the color development is carried out in the presence of a predominant proportion of the products of oxidation of the color developing agent.

It is still another object of this invention to provide a novel process for preparing direct positive color images.

It is also an object of this invention to provide a novel color diffusion transfer process for producing direct positive full-color images.

It is likewise an object of this invention to provide a novel photographic element suitable for use in preparing direct positive color images by a photographic diffusion transfer process.

These and other objects are attained by means of this invention as described hereinafter with reference to preferred embodiments thereof.

The present invention concerns light-sensitive photographic elements having coated thereon at least two Color-Forming Units as described herein and which elements can be processed in the presence of alkaline color developing solutions containing aromatic primary amino color developing agents to prepare direct positive color images.

The Color-Forming Units of the invention comprise:

Component A.-A hydrophilie colloid-silver halide emulsion capable of recording latent images on exposure to light;

Component B.A nondiffusible hydrophilic hydroquinone compound capable of releasing a ditfusible mercap' tan development inhibitor when the hydroquinone crossoxidizes with oxidized color developer, such development inhibitor releasing hydroquinones being referred herein as DIR compounds. This DIR compound is utilized in the color forming unit;

Component C.An emulsion of a hydrophilic colloid and a water-insoluble metal salt developable to substantial density without exposure to light, and which is referred to herein as a spontaneously developable emulsion;

Component D.A nondifiusible photographic color coupler capable of forming a ditfusible acid dye on development with an alkaline color developing solution containing an aromatic primary amino color developing agent, and which difi'usible-dye-releasing coupler is referred to herein as a DDR coupler;

Component D.A nondiffusible photographic color coupler capable of forming a nonditfusible dye on development with an alkaline color developing solution containing an aromatic primary amino color developing a ent.

Whensuch Color-Forming Units are exposed, a latent image (negative image) pattern of developable silver halide is formed in the light-sensitive emulsion (Component A). When this exposed emulsion is developed in an alkaline color developing solution containing an aromatic primary amino color developing agent in the presence of a DIR compound (Component B), the DIR compound reacts with color development oxidation product to release a dittusible mercaptan development inhibitor. The resulting ditfusible development inhibitor diffuses imagewise to the spontaneously developable emulsion (Component C) inhibiting development in regions corresponding to the latent image pattern (negative image area) formed in the light-sensitive emulsion. A coupler (Component D or D) is contiguous to the developable metal salt of the spontaneously developable emulsion. The developable metal salt of the spontaneously developable emulsion in regions not inhibited against development by the diifusible development inhibitor (positive image area) develops and a dye image .is formed in such regions when the coupler reacts with color development oxidation product. When DDR couplers are used (Component D), the resulting acid dye diffuses imagewise in register to a juxtaposed reception layer containing a mordant for acid dyes to produce a positive color reproduction. When conventional couplers are used (Component D), the resulting image dyes are non-dii'rusible and remain in the photoelement. This photoelement must then be bleached and fixed to remove the developed silver and residual silver halide, thus leaving only the non-ditfusible dye image.

1 Le. either DDR type or conventional type.

The Color-Forming Units are prepared so that the light sensitive emulsion develops and a development inhibitor is released from the DIR compound a finite time prior to the development of the spontaneously developable emulsion and the subsequent formation of the image dye. Such can be accomplished by physically dis-- posing the light-sensitive emulsion (Component A) and the contiguous DIR compound (Component B) further from the support than the spontaneously developable emulsion, by utilizing a silver halide emulsion having a shorter development induction period for the light-sensitive emulsion than the developable metal salt in the spontaneously developable emulsion, and/ or by utilizing DIR compounds that react at a faster rate than the couplers.

The couplers and DIR compounds are integral components of the present elements. The DIR compounds can be incorporated either in, or in a layer contiguous to, the light sensitive emulsion, and the coupler (DDR or conventional type) can be incorporated either in, or in a lay er contiguous to, the spontaneously developable emuls-1on.

Photographic elements suitable for preparing correct full-color positive renditions can be prepared by utilizing three of the present Color-Forming Units wherein the light sensitive emulsions are sensitive to red, green and blue light respectively, and the couplers capable of forming dyes complementary to the color of the spectral sensitivity of the respective Color-Forming Units. However, false sensitization can also be utilized in preparing the present photographic elements.

The DDR or diifusible-dye-releasing couplers used in the photographic elements of the invention are initially nondiifusing in the layers of the element but form dyes diffusible in the layers of the element on reaction with oxidation products of aromatic primary amino silver halide photographic color developing agents. Such DDR couplers include those having the formulas:

DYE-LINK- (COUP-BALL) n and BALL-LINK- COUP-SOL) EALL-LINK-COUP wherein (1) DYE is a dye radical containing an acidic solubilizing radical;

(2) LINK is a connecting or linkage radical such as azo (-N:N), azoxy O (N=1 mercuri (I-Ig-), oXy (O-), alkylidene (includes both CH. and :CH-), monothio (-S) or dithio (3) COUP is a photographic color coupler radical such as a S-pyrazolone coupler radical, a phenolic coupler radical or an open-chain kctomethylene coupler radical, the coupler radical being substituted in the coupling position with the connecting or linkage radical;

(4) BALL is a photographically inert organic radical of such molecular size and configuration as to render the coupler nondiifusing in the element in the alkaline color developing solution;

(5) SOL is either a hydrogen atom or an acidic solubilizing group when the color developing agent contains an acidic solubilizing radical, SOL always being an acidic solubilizing radical when the color developing agent is free of an acidic solubilizing group; and

(6) n is an integer of l or 2 when LINK is an alkylidene radical, and n is always 1 when LINK i one of the other aforementioned connecting radicals, namely, azo, azoxy, mercuri, oxy, thio, or dithio.

The acidic solubilizing radicals described above can be attached to the coupler and/or developer moieties of the dyes, and render the dyes difiusible in the element in alkaline processing solutions. Typical of such radicals i are carboxylic, sulfonic, ioniza ble sulfonamido, and hydroXy-substituted groups that lend to dyes negative charges.

Typical dye radical substitutents (DYE) of the DDR couplers include azo, azomethine, indoaniline, indophenol, anthraquinone and related dye radicals well known in the art that exhibit selective absorption in the visible spectrum. The dye radicals contain acidic solubilizing moieties.

When DDR couplers having the formula DY E-LINK- (COUP-BALIJ as described above are reacted with oxidized color developing agent, the connecting radical (LINK) is split from the coupler moiety and a diffusible preformed acid dye (DYE) is released which diffuses imagewise to a reception layer. An acidic solu bilizing group on the preformed dye lends ditfusiblity and mordantabiiity to the dye molecule. The coupling portion of the DDR coupler (COUP) couples with color developing agent oxidation product to form a dye that is nondiffusible in the element because of the attached ballasting group (BALL) in a noncoupling position. In this type of DDR coupler, the color of the diifusible dye is determined by the color of the preformed dye moiety (DYE), the color of the reaction product of color developer oxidation prodnet and the coupler moiety (COUP) being unimportant to the color of the ditfusible image.

When DDR couplers having formula BALL-LINK- (COUP-SOL) as described above are reacted with oxidized color developing agent, the connecting radical (LINK) is split from the coupler moiety and a diffusible dye is formed with the color developing agent oxidation product and the coupling portion (COUP) of the DDR coupler, which dye diffuses imagewise to a reception layer. Diffusibility is imparted to the dye by an acidic solubilizing group attached to a noncoupling position of the coupling portion (COUP) of the DDR coupler and/or to the color developing agent. The ballast portion of the DDR coupler remains immobile. In this type of DDR coupler, the color of the diffusible dye is determined by the color of the reaction product of color developer oxidation product and the coupler moiety (COUP).

When the coupler radical (COUP) in the DDR couplers is a S-pyrazolone radical, we prefer to have substituted in the 3-position of the pyrazolone moiety an anilino group or an alkoxy group. When the coupler radical (COUP) in the DDR couplers is a cyan-forming phenolic coupler radical, we prefer to have substituted in the ortho or 2-position of the phenolic moiety a fully substituted amido group (e.g.,

wherein R is an alkyl group or a phenyl group). Also, when the connecting radical (LINK) in the DDR couplers having the formula, BALL-LINK-(COUP-SOL),,, is an azo radical, we prefer that the ballasting radical (BALL) be a phenyl radical containing either a hydroxy group or an amino group (NI-I substituted in the ortho or 2-position of the phenyl moiety.

Typical conventional cyan, magenta and yellow forming couplers useful in this invention to form non-diifusible dyes on coupling with oxidation products of color developing agents may be found, for example, in the following US. patents:

Cyan: 2,895,826, Salminen et al., July 21, 1959; 2,474,293, Weissburger et al., lune 28, 1949; 2,908,573, 2,908,573, Bush et al., October 13, 1959.

Magenta: 2,600,788, Loria et al., June 17, 1952; 2,908,573, Bush et al., October 13, 1959.

Yellow: 2,875,057, McCrossen et al., February 24, 1959; 2,908,573, Bush et al., October 13, 1959.

These non-ditfusible-dye-forming couplers are represented by the following formula: BALL-COUP wherein BALL and COUP are as defined above and BALL is attached to the coupler in a non-coupling position.

Non-ditfusible couplers of the formula BALL-LINK- COUP can be used when the color developing agent is supplied with a solubilizing function.

The DIR, development inhibitor releasing, hydroquinone compounds used in the photographic elements of the invention release development inhibiting mercaptans that are dilfusible in the layers of the Color-Forming Unit. It is believed that the DIR hydroquinone compound cross-oxidizes with the oxidation product of aromatic primary amino silver halide developing agents. As a result of this cross-oxidation reaction, the hydroquinone is oxidized to the corresponding quinone. It is from this quinone only that the diifusible development inhibiting mercaptan is split.

The DIR compounds of this invention are non-diffusiblc, or ballasted, thio-substituted hydroquinones which react with oxidized color developing agent to form a diffusible mercaptan development inhibitor. If desired, thio-substituted hydroquinone compounds of this invention can be masked with an alkaline splittable group. That is, one or both of the hydroxyl groups of the hydroquinone can be replaced with any suitable substituent, such as an acyl group, which splits off under alkaline conditions to regenerate the hydroxyl group. A masking group inactivates a hydroxyl group of the hydroquinone compound. Masked hydroquinone compounds can be incorporated directly in light sensitive silver halide systems. Typical useful DIR compounds of this invention include:

Sol-Ball S-Rad Especially useful thio-substituted hydroquinones are the X-(5-tetrazolylthio) hydroquinones and the X-(Z-benzoxazolyl) hydroquinones, such as compounds I through VI, below. The xin these names indicates that the substituent can be in any available position on the hydroquinone nucleus.

Ball is a ballast group as described above for DDR couplers.

S01 is an acidic solubilizing group as described above for DDR couplers.

S- is a monothio radical which is split from the DIR compound when said compound cross-oxidizes with oxidized color developer. This S- radical forms with Rad a diiiusible mercaptan development inhibitor when the S is split from the DIR compound.

Rad includes a wide variety of photographically inert carbon containing heterocyclic radicals that are diffusible in the layers of the Color-Forming Unit and form mercaptans with the monothio connecting or linking radical when the connecting radical is split from the quinone of the DIR hydroquinone compound. I

Typically such radicals generally contain at least one hetero nitrogen, oxygen or sulfur atom, and preferably, 1 to 4 hetero nitrogen atoms. The hetero nitrogen atoms in the heterocyclic radicals have no hydrogen atom attached thereto as the RAD radical is photographically inert. Illustrative carbon-containing heterocyclic radicals include lphenyl-tetrazolyls, oxazolyls, oxadiazolyls, diazolyls, thiadiazolyls, benzoxazolyls, benzothiazolyls, pyridmidyls, pyridinyls, quinolinyls, and the like.

R=hydrogen, or any alkaline splittable masking group, such as an acyl group, e.g., acetyl, mono-, dior trichloroacetyl, mono-, dior trifluoroacetyl, perfiuoroacyl (e.g. butyryl), pyruvyl, alkoxalyl, nitrobenzoyl, cyanobenzoyl, etc.

R, as in R above.

Any combination of R and R may be used.

The nature of the ballast groups (BALL) in the DIR compounds and DDR coupler compounds described above is not critical as long as they confer nonditfusibility to these compounds. Typical ballast groups exemplified hereinafter in the specific compounds disclosed include long chain alkyl radicals or several short chain alkyl radicals having e.g. 8-22 carbon atoms, linked directly or indirectly to the coupler molecules, as well as aromatic radicals of the benzene and naphthalene series, etc., linked directly or indirectly to the coupler molecules by a splittable linkage, or by a removable or irremovable but otherwise nonfunctional linkage depending upon the nature of the coupler compound. Useful ballast groups generally have at least 8 carbon atoms.

With regard to the above-described coupler radicals (COUP) in the DDR couplers, the coupling position is Well known to those skilled in the photographic art. The S-pyrazolone coupler radicals couple at the carbon atom in the 4position, the phenolic coupler radicals, including ot-naphthols, couple at the carbon atoms in the 4- position and the open-chain ketomethylene coupler radicals couple at the carbon atom forming the methylene moiety, e.g.,

The term nondifiusing used herein :as applied to the couplers and coupler reaction products, has the meaning commonly applied to the term in color photography and denotes materials which for all practical purposes do not migrate or wander through organic colloid layers, such as gelatin, comprising the sensitive elements of the invention. The term diffusible as applied to the mercaptan development inhibitors released from the DIR compounds and the dyes released from the DDR couplers in the present processes has the converse meaning and denotes materials having the property of diffusing effectively through the colloid layers of the sensitive elements in the presence of the nondiffusing materials from which they are derived in alkaline color developing solutions.

The silver halide emulsion of the present photographic elements are conventional developing-out photographic silver halide emulsions including silver chloride, silver bromide, silver bromoiodide, silver chlorobrornide and silver chlorobromoiodide emulsions. There can be employed as the dispersing agent or substrate for the silver halide in its preparation, gelatin or some other commonly employed photographic hydrophilic colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound, although gelatin is preferred. Such hydrophilic colloidal materials can also be used in the non-light-sensitive layers in the subject elements in accordance with usual practice. Such hydrophilic colloids are well known in the art.

The subject photographic emulsions can contain the addenda generally utilized in such products including optical sensitizers, speed-increasing materials, antifoggants, coating aids, gelatin hardeners, plasticizers, ultraviolet absorbers and the like.

As described above, each Color-Forming Unit in the photographic elements of the invention contains, in addition to a light-sensitive silver hailide emulsion (Component A), an emulsion of a water-insoluble metal salt that is developable (i.e., reducible to metal) with alkaline color developing solutions containing aromatic primary amino color developing agents to a substantial density without light exposure of the element (Component C). Such metal salts are preferably Water-insoluble lightsensitive silver salts such as silver chloride, silver bromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, silver citrate, silver oxalate, silver phosphate, silver stearate, silver, ferrocyanide, silver cyanide, silver thiocyanate and the like. Other useful salts include palladium Denoting the coupling position.

bromide, palladium cyanide and related heavy metal salts, as well as cuprous bromide and the like. Such metal salts can be made spontaneously developable by incorporating in the emulsion a wide variety of well-known physical development nuclei. Typical development nuclei include colloidal noble metals such as silver and gold; colloidal metal sulfides, selenides and tellurides such as lead sulfide, nickel sulfide, cadmium sulfide, silver sulfide, silver selenide, silver telluride, copper sulfide, zinc sulfide and mercury sulfide; metal proteinates such as silver proteinates; sodium sulfide; colloidal sulfur; and such organic sulfur compounds as thiourea, and Xanthates. Conventional solvents for the metal salts are utilized in the developing compositions when the physical development nuclei are employed to make the emulsions spontaneously developable, including ammonium and alkali metal thiosulfates, thiocyanates, sulfites and the like. Another method that can be utilized to make the light-sensitive, water-insoluble salts spontaneously developable is by prefogging the emulsion with light or with chemical reducing agents such as alkali metal borohydrides and the like in accordance with well-known photographic fogging techniques.

A wide variety of alkaline color developing solutions containing aromatic primary amino color developing agents can be utilized to process the present photographic elements. Such developing solutions are utilized to develop or reduce to silver the exposed silver halide in the light-sensitive emulsions (Component A) to form a negative image, and to develop or reduce to a metal the metal salt in the spontaneously developable emulsion (Component C) to form a positive image. Particularly useful developing agents are the well-known p-phenylenediamine color developing agents. The color developing agent can be either incorporated in an alkaline photographic developing solution that is topically applied to the present photographic elements on processing, or the color developing agent can be incorporated in the element.

When the color developing agent is used in the present photographic elements, it is advantageous to use forms that have substantial stability in emulsions such as Schifi base derivatives of primary amino developing agents. Such Schifi bases are prepared by reacting primary amino developing agents with sulfonated, hydroxylated or carboxylated aromatic aldehydes of the benzene or naphthalene series. Such Schiff bases typically have the formula R-N CHR wherein R is an aryl radical such as a phenyl radical substituted in the ortho or para position with a hydroxyl group or an amino group (e.g. OH, NH NHR or N(R") wherein R" is a lower alkyl radical having 1 to 6 carbon atoms); and R is an aryl radical such as phenyl or naphthyl substituted with an acidic group such as carboxyl, sulfo, and hydroxy lower alkyl groups. A typical Schiff base color developing agent can be prepared by reacting 2-amino-5-diethylaminotoluene and o-sulfobenzaldehyde. Other Schiff base developers that are useful as such, as salts or as sulfur dioxide complexes include:

(1) N ethyl N (p hydroxyethyl) -4 (o-sulfobenzylideneamino)aniline sodium salt,

(2) N N diethyl 4(2,4 dihydroxybenzylideneamino)-3-methylaniline, and

(3) N ethyl 3 methyl-N-(B-methylsulfonamidoethyl)-4-(2-sulfobenzylideneamino)aniline sodium salt. Such incorporated developing agents can be activated by immersing the photographic element in an aqueous alkaline solution or by spreading an aqueous alkaline solution on the surface of the element. Such incorporated developing agents can be positioned in any layer of the present photographic elements from which the developing agents can be readily made available for development on activation with aqueous alkaline solutions. Generally, such incorporated developing agents are either incorporated in the light-sensitive silver halide emulsion layers or in layers contiguous thereto.

Typical supports comprising the photographic elements of the invention include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polyethylene film, polypropylene film, and related films of resinous materials, as well as paper, glass, and others.

In preparing the photographic elements of the inven tion, the above-described emulsion layers are coated on the photographic supports in the form of multilayer color photographic elements having at least two preferably three Color-Forming Units sensitive to difierent regions of the visible spectrum. The uppermost Color-Forming Unit is preferably selectively sensitive to blue light. Between the blue light-sensitive Color-Forming Unit and the other Color-Forming Units there is typically disposed a yellow dye layer of Carey Lea silver layer for absorbing or filtering blue radiation that may be transmitted through the uppermost blue sensitive layer. However, the physical disposition of the red, green and blue light-sensitive Color- Forming Units within the present photographic elements can be widely varied in accordance with usual practice. Such multilayer photographic elements can also have other interlayers or sublayers for specialized purposes in accordance with usual practice.

Barrier layers are used between each Color-Forming Unit to ensure that the activity of the development inhibiting mercapto compounds released by the DIR compounds are confined to a single Color-Forming Unit. Hence, the barrier layers contain a water-insoluble salt or metal capable of forming a water-insoluble salt with mercaptans, silver halides such as silver chloride, silver bromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, etc., being preferably used. Other compounds suitable for use in the present barrier layers that react With mercaptans include colloidal metals such as silver and gold; and colloidal metal sulfides, selenides and tellurides such as lead sulfide, nickel sulfide, cadmium sulfide, silver sulfide, copper sulfide, zinc sulfide, mercury sulfide, silver selenide, silver telluride and the like. The barrier layers containing light-sensitive silver salts are prepared to be substantially less sensitive to light than the light-sensitive emulsions in the Color-Forming Units. Such barrier layers also serve to prevent oxidized color developing agent from wandering from one Color-Forming Unit to another H where it could cause color contamination. Antioxidants such as n-o-ctadecyl hydroquinone and the like phenolic antioxidants, and nondiffusible photographic color couplers that form nondiffusible dyes on coupling with oxidized aromatic amino color developing agents can be utilized in the barrier layers to prevent wandering of such oxidized color developing agent.

The reception layer used to receive the diffused dye images on color development of the photoelements of the invention can be either a separate sheet pressed in contact with the photoelement or a layer integral with the photoelement.

When the reception layer is a separate reception sheet, the development and transfer operations can be effected by bathing either or both the exposed photographic element and the mordanted reception sheet in the developing solution before rolling into contact with each other. Alternatively, a viscous developing composition can be placed between the elements for spreading in a predetermined amount across and in contact with the exposed surface of the sensiti e element so as to provide all of the solution required for the picture area. The viscous developing composition is desirably utilized in one or more pods integral with the photoelement or the reception sheet that can be readily ruptured when development is desired, suitable viscous developer utilization techniques being disclosed in US. Patents 2,543,181; 2,559,643; 2,647,049; 2,647,056; 2,661,293; 2,698,244; 2,698,798; and 2,774,668.

When the reception layer for receiving the diifusible dye is an integral part of the photosensitive assembly, it is also useful. A typical element of this type can comprise a support, a mordanted colloid layer thereon and the various emulsion layers described above coated thereover. When easily dissolved emulsions are used such as those containing polyvinyl alcohol or an alkali-soluble cellulose ether phthalate vehicles, or a wet or dry stripping layer containing such vheicles is provided between the emulsions and reception layer, the developed emulsion layers can than be readily separated from the reception layer leaving the dye image thereon. Similarly, the reception layer can be initially bonded to the outer emulsion surface. In this case, it is preferred to expose through the support of the sensitive element unless the reception layer itself is transparent. Such photoelements can be processed in the same manner as those not containing integral reception layers.

The reception layers in the photoelements of the invention can contain any of the conventional mordant materials for acid dyes. The reception layer can contain mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone described in the Minsk U.S. Patent 2,882,156 granted Apr. 14, 1959. Other mordants include the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in Sprague et al., U.S. Patent 2,484,430 granted Oct. 11, 1949 and cetyl trimethylammonium bromide, etc. Particularly effective mordanting compositions are described in copending applications of Whitmore, U.S. Ser. No. 211,095, filed July 19, 1962, now U.S. Patent 3,271,148, and Bush, U.S. Ser. No. 211,- 094 filed July 19, 1962, now U.S. Patent 3,271,147. The mordanting compositions described in the Knechel et al., application comprise at least one hydrophilic organic colloid containing a finely-divided, uniform dispersion of droplets or globules of a high-boiling, water-immiscible organic solvent in which is dissolved a high concentration of a cationic nonpolymeric, organic dye-mordanting compound for acid dyes. The mordanting compositions described in the Bush application comprise at least one hydrophilic organic colloid containing a finely-divided, uniform dispersion of particles of asalt of an organic acidic composition containing free acid moieties and a cationic, nonpolymeric, organic dye-mordanting compound for acid dyes. Useful cationic or basic organic dye-mordanting compounds for acid dyes include quaternary ammonium and phosphonium, and ternary sulfonium compounds in which there is linked to the N, P, or S onium atom at least one hydrophobic ballast group such as long-chain alkyl or substituted alkyl groups. Furthermore, the reception layer or sheet can be sufiicient by itself to mordant the dye as in the case of the use of a sheet or layer of a polyamide or related polymeric material.

Reception sheets for the dye images, as Well as the photoelements of the invention can contain ultraviolet absorbing materials. In the reception sheets, ultraviolet absorbers protect the mordanted dye images from fading and print-out due to ultraviolet light. In the photoelements, ultraviolet absorbers can serve as taking filters to reduce ultraviolet sensitivity. Typical ultraviolet absorbing materials are described in copending applications of Sawdey, U.S. Ser. Nos. 144,228 filed Oct. 10, 1961, now U.S. Patent 3,253,921 and 183,417 filed Mar. 29, 1962, now U.S. Patent 3,250,617. Illustrative useful ultraviolet absorbing materials disclosed by Sawdey have the formulas and wherein: R is-a phenyl group including such substituents as hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups or hydroxy groups; and R R and R are hydrogen atoms, hydroxyl groups, halogen atoms, nitro groups, alkyl groups, alkoxy groups, aryl groups or aryloxy groups. Other ultraviolet absorbing materials well known in the photographic art can also be utilized.

If desired, a keep-negative as well as a positive color transfer print can be prepared. In preparing such a color negative, a conventional photographic color coupler of the type that forms a nonditfusible dye when reacted with oxidized color coupler is utilized with the DIR compound. In this embodiment, DDR couplers are chosen that do not form colored nonditfusible dyes during the present process. Also, the reception layer used to receive the ditfused positive dye image is a separate receiving sheet not integral with the element. After the positive image is transferred to the receiving sheet, the remaining negative element is fixed in hypo to remove unexposed silver halide and bleached (i.e., with an alkali metal ferricyanide) to remove silver. Suitable photographic color couplers that form nonditfusible dyes are of the phenolic, S-pyrazolone and open-chain ketomethylene type such as those disclosed in Spence et al., U.S. Patent 2,640,706; Weissberger et al., U.S. Patent 2,407,210; and Weissberger et al., U.S. Patent 2,474,293.

The drawings illustrate in section and in elevation typical photographic elements of the invention.

FIG. 1 illustrates a typical photographic element of the invention wherein the DIR compound is positioned in the light-sensitive silver halide emulsion and the spontaneously developable emulsion comprises a nu cleated metal salt in each Color-Forming Unit.

FIG. 2 illustrates a typical photographic element of the invention wherein the DIR compound is positioned in the light-sensitive silver halide emulsion and the spontaneously developable emulsion comprises a fogged silver halide emulsion in each Color-Forming Unit.

In FIG. 1, over photographic support 10 are coated three Color-Forming Units of the invention that are sensitive to diiferent regions of the spectrum. Over support 10 is coated nucleated metal salt layer 11 containing a cyan-forming DDR coupler. Over layer 11 is coated. a silver halide emulsion that is sensitive to red light and. a DIR compound. Over layer 12 is coated barrier layer 13 containing a compound capable of forming an in soluble salt with mercaptans. Over layer 13 is coated nucleated metal salt layer 14 containing a magenta-forming DDR coupler. Over layer 14 is coated silver halide emulsion layer 15 that is sensitive to green light and a DIR compound. Over layer 15 is coated barrier layer 16 containing a compound capable of forming an in soluble salt with mercaptans and a yellow filter material. Over layer 16 is coated nucleated metal salt layer 17 containing a yellow-forming DDR coupler. Over layer 17 is coated a silver halide emulsion layer 18 that is sensitive to blue light and a DIR compound.

With respect to FIG. 2, on photographic support 20 are coated three Color-Forming Units of the invention that are sensitive to different regions of the visible spectrum. On support 20 is coated fogged silver halide emulsion layer 21 containing a magenta-forming DDR coupler. Over layer 21 is coated silver halide emulsion layer 22 that is sensitive to green light and contains a DIR compound. Over layer 22 is coated barrier layer 23 containing a compound capable of forming an insoluble salt with mercaptans. Over layer 23 is coated fogged silver halide emulsion layer 24 containing a cyanforming DDR coupler. Over layer 24 is coated silver halide emulsion layer 25 that is sensitive to red light and contains a DIR compound. Next, barrier layer 26 containing a compound capable of forming an insoluble salt with mercaptans and a yellow filter material is coated. Over layer 26 is coated fogged silver halide emulsion layer 27 containing a yellow-forming DDR 11 12 coupler. Over layer 27 is coated silver halide emulsion 2-{4-[3-(4-tert-amy1- X sulfophen0xy)benzamido]phenlayer 28 that is sensitive to blue light and contains a DIR ethyl}-x-(1-phenyl-S tetrazolylthio)hydroquinone dicompound. Over layer 28 is coated protective layer 29. acetate sodium salt dihydrate Iv. C|)COCH5 0 Ba 0 mQ-mm 0 n l Q 0- -05H,,-c

l oooona some-2&0

The development inhibitor releasing compounds (DIR 15 compounds) used in my invention are described by the following specific examples:

2{4-[3-(4-tert-amyl X sulfophenoxy)benzamido]phenethyl}-x- 1-phenyl-5-tetrazoly1thio)hydroquinone sodi- I urn salt 20 5-[4-(3,5 disulfobenzamido)phenethyl] 2-methyl-3-(1- 2-[4-(3,5-disulfobenazmido)phenethyl] x (l-phenyl-S- phenyl-S-tetrazolylthio)hydroquinone disodium salt c tetrazolylthio)-hydroquinone disoduim salt dihydrate II. IIT N CaH5-N N G5 2- [4- 3 ,5 -disulfobenzamido phenethyl] -X- (2-benzox azolylthio)hydroquinone disodium salt dihydrate VI. OH s oaNa-mo soaNa-Hzo 13 The following synthesis illustrates the preparation of a representative DIR hydroquinone compound of my invention.

amido]phenethyl}-x-(I phenyl 5 tetrazolylthio)hy droquinone sodium salt Intermediate #1 .4-triflu0r0acetamid0phenethylhydroquinone 143 parts of 4-aminophenethylhydroquinone were added to 600 volumes of trifluoroacetic anhydride. The clear mixture was refluxed for 5 minutes on a water bath and poured slowly into 3000 volumes of water whereupon the product separated in the form of a tan solid which was filtered ofif and dried.

Intermediate #2.-4-triflu0r0acetamidophenethylbenzoquinone 40 parts of Intermediate #1 was dissolved in 1000 volumes of acetone and 60 volumes of H 0. To this solution was added dropwise at 10 21 solution of 60 volumes of concentrated H 80 in 100 volumes of H over a period of 20 minutes. To this solution was added dropwise at over a period of 20 minutes a solution of 18 parts of potassium dichromate in 100 volumes of H 0. This mixture was stirred for 5 minutes after which time 2000 volumes of water were added whereupon the product separated. This mixture was stirred for 1 hour and the solid product was filtered off and dried.

Intermediate #3.-X-(1-phenyl-5-tetraz0lylthio -2- (4- trifluoroacetamidophenethyl) hydroquinone To a solution of 48.5 parts of Intermediate #2 in 500 volumes of chloroform under nitrogen was added with stirring 27 parts of 1-phenyl-5-mercaptotetrazole. This mixture was refluxed under nitrogen for 3 hours during which time solution occurred and the product separated in the form of a white solid. This solid was filtered off and dried.

Intermediate #4 .2- (4-amin0phenelhyl -x- (1 -phenyl- 5 -tetrazolylthi0 hydroquinone To a solution of 25 parts of Intermediate #3 in 500 volumes of 90 percent ethyl alcohol under nitrogen was added 25 volumes of 20 percent NaOH. The clear reaction mixture was let stand overnight at room temperature under nitrogen, after which time it was poured into 2000 volumes of dilute acetic acid. The tan solid, which separated, was filtered ofi and dried.

Intermediate #5.2 {4 [3 (4 t amyl x chlorosulfonylphenoxy benzamido] phenethyl}-x-(1-phenyl-5- tetrazolylthio)hydroquinone To a solution of 16 parts of Intermediate #4 and 5 parts of N,N-dimethylaniline in 500 volumes of dry acetone was added at 40 with stirring, a solution of 16 parts 1 Couplers VII to XVI below are substituted in the coupling position with preformed yellow dyes that are split from the ballasted couplers and become diifusible when said couplers react with oxidized color developers. 1-hydroxy-4-{3-[4-(N-ethyl-N-fl-sulfoethylamino)-2- phenoxy)butyl] -2-naphthamide sodium salt.

VII. OH

1-hydroxy-4-{4-[ 1-(4-sulfophenyl)-3-methyl-4-pyrazol-5- onylazo]-3 -sulfophenylazo}-N-[5-(2,4-di-tert-amylphenoxy)buty1] -2-naphthamide disodium salt.

1-hydroxy-4-{3-[4-(N ethyl N-li-carboxyethylaminc)- Z-methylphenylazo] phenylazo} -N- [6-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide sodium salt.

IX. on

( sHu-ii 1 7 1 8 l (p t butylphenoxyphenyl)-3-[oc-(4-t-butylphenoxy) Each of the Couplers XVII to LH below contain an propionamido] 4 (2 bromo-4-methylamino-j-sulfoacid solubilizing group in a noncoupling position and on 1-anthra9,10-quinonylazo)-5-pyrazolone coupling with oxidized color developer forms a nondiffuson {3 [u-(2,4-di-tert-amylphenoxy)acetamido]benzoyl}- 25 ible dye by the elimination of a ballasting group from the a {3 [4-(N-ethyl-N-B-sulfoethy1amino)-2-methy1- coupling position as a. direct result of said coupling reacphenylazo1phenylazo} Z-methoxyacetanilide sodium tion. salt N t-C5Hn 0 01120 ONH l 0 CH3 L CaHn-t I Ca s N=N N\ CzH4SOaNa 0H,

1 hydroxy 4-{4-[1-(4-sulfophenyl)-3-carboxy-4pyra- Couplers XVII to XXXV below form diffusible cyan zol 5 onylazo]-3-sulfophenylazo}-N{4-[a-(2,4-di- 45 dyes. tert amylphenoxy)butyramido1phenyethy1} 2 naphthamide XVI.

O H CsHn-l? SOaH 25 Couplers XLVIII to LII below form difiusible yellow dyes.

a-B enzoyl-a- 4-hydroxy-2-pentadecylphenylazo) -4( 3- sulfobenzalnido)acetanilide sodium salt XLVHI.

a-BCHZOYl-oc- (4-l1ydroxy-2-pentadecylphenylazo) -4- 3,5 disulfobenzamido)acet-anilide dipotassium salt XLIX.

a-Benzoyl-a- [4- 3 -metl1yl-5-pentadecy1) pyrazolylazo] -4- (3,5-disulfobenzamido)acetanilide dipotassium salt L.

oc-B61'1ZOyl-oc-(3 -oct adecylcarbamylphenylthio) 3,5-dicarboxyacetanilide a-Pivalyl-a- 3-octadecy-lcarbamylphenyl thio 4-sulfoacetani1ide potassium salt LII.

CONE CHE Diffusible dyes are formed when the above listed (i.e. VII to LII) non-diffusing couplers are employed in the process of the invention with well-known p-pheuylenediamine developing agents, e.g., N,N-cliethylp-phenylenediamine, 2-amino-5-diethylamino toluene, N-ethyl-fi-metb anesulfonamidoethyl-3-methyl-4-arninoaniline, and other 26 N,N-dialkyl-p-phenylenediamine developing agents described by Bent et al. J.A.C.S. 73, 3100-3125 (1951).

Couplers LIII to LXI are nondifiiusible couplers which can also be used in the process of my invention when the color developing agent is supplied with the alkali solubilizing function.

Couplers LIII to LVI below form diffusible cyan dyes.

1-hydroXy-4- 4-octadecyloxyphenylazo) -N-methyl-2- naphthanilide LIII.

l 0 OISHIU 1-hydroXy-4-dodecyloxy-Z-naphthanilide LIV.

1-hydroxy-4- (Z-amino-4-octadecylphenylazoxy) -2- naphtharnide LV.

CONE:

1-hydroxy-2',5'-dibutoxy-4- [4-(sulfomethyl) phenylazo1- 2-naphthauilide 27. Couplers LVII to LIX below form diffusible magenta dyes.

1-phenyl-3-methyl-4- (4-octadecyloxybenzylidene)-5- pyrazolone LVII.

4,4'-thiobis(1-phenyl-3-methyl-5-pyrazolone) LVIII.

(3113 Cl 113 N=C C=N Q l l -Q Couplers LX and LXI below form diffusible yellow dyes.

oc,oc'- (4-octadecyloxybenzylidene) bis abenzoylacetanilide] Representative color developing agents possessing the solubilizing functions useful with the nondiffusing couplers above are as follows:

When the DDR couplers given above were incorporated into exposed silver halide emulsions that were developed in contact with a mordanted reception layer using an alkaline color developing composition containing the developing agent 4-an1ino-N-ethyl-N-( B-hydroxyethyl)aniline, the following colors of dye images were obtained on the reception layer from the respective couplers:

VII yellow VIII yellow IX yellow X orange-yellow XI yellow XII yellow XIII yellow XIV yellow XV yellow XVI yellow XVII cyan XVIII cyan XIX cyan XX cyan XXI cyan XXII cyan XXIII cyan XXIV cyan XXV cyan XXVI cyan XXVII cyan XXVIII cyan XXIX cyan XXX cyan XXXI cyan XXXII cyan XXXIII cyan XXXIV I- cyan XXXV cyan XXXVI magenta XXXVII magenta XXXVIII magenta XXXIX magenta XL magenta XLI magenta XLII magenta XLIII magenta XLIV magenta XLV magenta LXVI magenta XLVII magenta XLVIII yellow XLIX yellow L yellow LI yellow LII yellow The following syntheses illustrate the methods for preparations of representative DDR couplers of my invention.

Coupler VII. 1-hydr0xy-4-{3-[4-(N-ethyl-N-[3-sulf0- ethylamino) 2 methylphenylazo]phenylazo} N [8- (2,4 di tel-t amylphen0xy)butyl] 2 naphthamide sodium salt To 200 ml. of concentrated sulfuric acid at 10 C. was added with stirring 17 grams of Intermediate C below. To the resultant solution was added dropwise over a period of 30 minutes at -5 C. with stirring a solution of 3.5 grams of sodium nitrite in 35 ml. of concentrated sulfuric acid (i.e. nitrosyls-ulfuric acid solution). This solution was stirred for a total of two hours after which time it was poured on to crushed ice. This solution was then added to a solution of 21 grams of 1-hydroxy-N-[5-(2A- di-tert-amylphenoxy)butyl]-2-naphthamide (US. Patent 2,474,293), in two liters of pyridine over a 30-minute period with stirring at 05 C. After 12 hours at room temperature the reaction mixture Was mixed with 1.5 kg. of crushed ice and acidified with concentrated hydrochloric acid. The red solid which separated was collected, washed with water and recrystallized twice from glacial acetic acid, yielding the product.

20 Coupler VII: Intermediate A.N-etlzyl-3-metlzyl-N-(flsulfoethyl)mziline sodium salt A mixture of 675 grams of N-ethyl-toluidine and 528 grams of sodium 2-bromoethane sulfonate was heated at 160190 C. for 3 /2 hours, after which time mixture was cooled and 1200 n11. of water was added. The solution was made alkaline with sodium hydroxide and the solid which separated was collected, washed with acetone and ether and recrystallized from 2.5 liters of ethyl alcohol, yielding 420 grams of product.

Coupler VII: Intermediate B.-,B-{N etlzyl-N- [fl-methyl- 4-(3 -nitr'plzenylaz0)plzenyl]amino}-ethylsulf0nic acid sodium salt Coupler VII: Intermediate C.,8-{N-[4-(3-aminoplzenylazo)-3-metlzylphenyl] -N-etlzylamin0}ethyl sulfonic acid sodium salt To a solution of 41 grams of Intermediate B above in 2 liters of water at 90 C. was added over a period of 30 minutes a solution of 40 grams of 60 percent sodium sulfide in 150 ml. of water. The mixture was refluxed for an additional 2%. hours during which time approximately /2 of the Water Was distilled off. This mixture was filtered and refrigerated over night during which time a solid separated. The solid was collected and recrystallized from 200 ml. of ethyl alcohol, yielding the product.

Coupler XIII: I-hyclroxy-4-{4- [3-metlzyl-4-(1,5-rlisulfo-3- naph thylaz0)-I -pyrazol-5-0nyl] phenylazo} N [5(3- penzadecylphenoxy)butyl] 2 naplzthamide disorlium salt A solution of 6.5 grams of sodium nitrite in 93 ml. of water was added to a solution of 49.5 grams of Intermediate E below in 300 ml. of five percent sodium carbonate solution. This mixture was cooled to C. and added to a well-stirred mixture of 75 ml. concentrated hydrochloric acid and 150 grams of ice. After 1 /2 hours, the diazonium suspension was added in portions with vigorous stirring to a solution of 44.4 grams of Intermediate C below in a mixture of 1500 ml. of ethyl alcohol and 55 grams of potassium carbonate in 360 ml. water. After two hours, the crude product was filtered, triturated in boiling ethyl alcohol, then dissolved in 1500 ml. ethyl alcohol and 1500 ml. of 3 percent potassium carbonate solution. The dark orange solution was filtered and acidified with acetic acid. The solid which separated was filtered, triturated in acetone and benzene, extracted twice with hot water, and recrystallized from a 1:1 n-propyl alcohol-water mixture, yielding 40 grams of product, M.P. 270 C.

Coupler XIII: Intermediate A .'y (3-penlarlecylphenoxy) butyronitrile A mixture of 4 grams of sodium hydroxide and 31 grams of 3-pentadecylphenol (Minn. Mining and Mfg. Co.) in 100 ml. of xylene was refluxed for 6 hours during which time 1.8 ml. of water was distilled off. To the mixture was added 11 grams of chlorobutyronitrile dropwise over 1 hour after which time the mixture was refluxed for 7 hours. The xylene was then distilled off over a 12 hour period and the residual oil was poured into 25 ml. of dilute hydrochloric acid. The Waxy solid which separated was collected and recrystallized from 100 ml.

30 of acetonitrile, yielding 23 grams of product, M1. 46-- 47 C.

Coupler XIII: Intermediate B.5(3-pentadecylpl1en0xy) bulylamine A mixture of 5 grams of Intermediate A above, 3 ml. of ethyl alcohol, 5 ml. of liquid anhydrous ammonia and 0.1 gram of Raney nickel was heated for 12 hours at C. under a hydrogen atmosphere at a pressure of 2200 p.s.i. The cooled solution was filtered and concentrated in vacuo. The residual oil was distilled at 165 C. at 9 microns, yielding the product.

Coupler XIII: Intermediate C.-I-hydr0xy-N-[6-(3-pentadecylphenoxy) butyl] -2-naphtliamide A mixture of 5 grams of phenyl 1-hydroxy-2naphthoate and 7 grams of Intermediate B above was heated at 150 C. for /2 hour in vacuo during which time phenol was collected from the mixture. The residual oil was poured into 100 ml. of petroleum ether whereupon a crystalline solid separated. This solid was collected and recrystallized from 90 ml. of ethyl alcohol, yielding 8 grams of product, M.P. 6466 C.

Coupler XIII: Intermediate D.-1 (4 nitrophenyl)-3- methyl-4- (1,5-disulf0-3-naphthylazo -5-pyrazol0ne disodium salt To a solution of 2.8 grams of 1-(4-nitrophenyl)-3 methyl-S-pyrazolone, 0.5 grams of sodium hydroxide and 7 grams of sodium acetate in 40 ml. of water was added 20 C. over a period of 20 minutes a diazonium mixture consisting of 1.1 gram of Z-amino-l,S-naphthalenedisulfonic acid disodium salt, 1.4 gram of sodium nitrite, 2. ml. of concentrated sulfuric acid and 10 ml. of water. The mixture was stirred for 1 hour at room temperature and heated over steam until all solids dissolved. The solution was cooled to 5 C. whereupon a red solid separated and was collected, yielding 4.5 grams of product.

Coupler XIII: Intermediate E.-I (4-aminophenyl)-3- methyl 4 (I,5-disuljo-3-naphthylaz0)J-pyrazolone disodium salt To a mixture of 31 grams of Intermediate D above in 32 ml. of Water at 90 C. was added over a period of 20 minutes a solution of 18 grams of 60 percent sodium sulfide in 40 ml. of water. The mixture was heated at reflux for an additional 2 hours after which time it was cooled to 50 separated was collected and recrystallized from 250 ml. of 10 percent brine solution, yielding 15 grams of product, M.P. 250 C.

Coupler X VII 1-lzydr0xy-4-stear0yloxymercuri-Z- naphthoic acid To a solution of 9.4 grams of 1-hydroxy-2-naphthoic acid (I.A.C.S. 64, 799 (1942)) in 200 ml. of dioxiane was added a solution of 38 grams of mercuric stearate in 500 ml. of dioxane. The mixture was heated over steam for 5 hours during which time a white solid separated. This solid was collected, washed with hot methyl alcohol and dried, yielding 30 grams of product.

Coupler XVIII: 1-hydroxy-4-d0d cyloxy-Z-naphthoic acid To a suspension of 2 grams of 1,4-dihydroxy-2-naphthoic acid (J.A.C.S. 64, 799 (1942)) in 40 grams of lauryl alcohol was added dry hydrogen chloride gas at 90 C. over a period of 11 hours while stirring. The clear reaction mixture was left at room temperature over night during which time a white solid separated. This solid was filtered, slurried in 50 volumes of petroleum ether, refiltered and dried, yielding 1.25 grams of product, M.P. -136 C.

C. and acidified with acetic acid. The solid which C upler XXI: I-hydroxy-N-(fi-sulf ethyl)-4-(4-0ctadecylaxyphenylazv)-2-naphtlzamide potassium salt To a solution of 51 grams of potassium hydroxide and 63 grams of Intermediate A below in 350 ml. of water and 1700 ml. of ethyl alcohol was added at C. over a period of 1 hour, a diazonium solution consisting of 72 grams of Intermediate B below, 120 grams of p-toluene sulfonic acid, and grams of isoamylnitrite in 2 liters of n-propyl alcohol. The mixture was stirred at room temperature for 5 hours after which time 3 liters of water were added and the mixture brought to reflux. The hot solution was filtered, acidified with glacial acetic acid and cooled whereupon a solid separated. The solid was collected, recrystallized from 1.5 litres of nbutyl alcohol, yielding 80 grams of product, M.P. 228-3 0 C.

Coupler XXI Intermediate A .--1-hydr0xy-N-(fi-sulf ethyl)-2-naphthamicle potassium salt A mixture of 132 grams of phenyl l-hydroxy-2-naphthoate, 1 liter of ethyl alcohol, 57.5 grams of taurine, 300 ml. of water and 28 grams of potassium hydroxide was refluxed for 15 hours after which time the solution was cooled and the solid which separated was collected, washed with ethyl alcohol, recrystallized from H 0 and dried, yielding 71 grams of product, M.P. 284-286 C.

Coupler XXI: Intermediate B.-4-0ctadecyloxyaniline A mixture of 39 grams of 4-nitrophenyloctadecyl ether (J.A.C.S. 73, 458 (1951)) and 0.5 gram of 10 percent palladium on charcoal in 300 ml. of ethyl alcohol was heated at C. for /2 hour under a hydrogen atmosphere at a pressure of 50 p.s.i.

The catalyst was filtered from the hot solution which was then chilled whereupon a solid separated. This solid was collected, and dried, yielding 32 grams of product, M.P. 78-81 C.

The preparations for couplers XXIV, XXV, XXVI and XXVII are given in copending application U.S. Ser. No. 154,841, filed Nov. 24, 2961, now abandoned.

Coupler XXX: 2-(3,5-disulf0benzamid0)-4-(4-lzydr0xy- Z-pentadecylphenylazo) 5-methylphenol dipotassium salt Coupler XXXVI: 1-phenyl-3-(3 sulf0benzamid0)-4-(4- octadecyloxyphenylazo)-5-pyraz0lone sodium salt To a solution of 3.6 grams of Intermediate 13 below and 2 grams of sodium hydroxide in ml. of 90 percent ethyl alcohol at 0 C. was added with stirring a diazonium solution consisting of 3.6 grams of 4-octadecyloxyaniline (Intermediate B of Coupler XXI above), 5.7 grams of p-toluenesulfonic acid monohydrate and 1.5 grams of isoamylnitrite in 100 ml. of n-propyl alcohol at 20 C. The mixture was stirred at room temperature for 3 hours after which time 25 ml. of water was added and the mixture was acidified with acetic acid. To this solution at 90 C. was added 100 grams of sodium chloride and the resultant solution was filtered and cooled. The solid which separated was collected, washed with water and dried, yielding 6 grams of product, M.P. 198-200 C.

32 Coupler XXXVI: Intermediate A.--1-phenyl-3-(3- chl0r sulf0nylbenzumido)-5-pyruz0l0ne To a solution of 88 grams of l-phenyl-3-amino-5-pyrazolone in 400 ml. of diethyl oxalate at 90 C. was added with stirring grams of m-chlorosulionyl'benzoyl chloride. The mixture was heated for /2 hour, cooled to 20 C. and the solid which separated was collected, triturated in water, ethyl acetate and dried, yielding 98 grams of product, M.P. 176177 C.

C upler XXXVI: Intermediate B.-1-plzenyl-3-(3- sulfonbenzamid -5-pyraz0l0ne A mixture of 58 grams of Intermediate A above in 250 ml. of 10 percent sodium hydroxide was stirred at room temperature for 2 hours after which time the solution was acidified with concentrated hydrochloric acid whereupon a solid separated. This solid was collected, washed with water and dried, yielding 23 grams of product, M.P. dec. 292 C.

Couplers XXXVII and XXXVIII were each prepared according to the procedure given for coupler XXXVI above using the appropriate intermediates.

Coupler XXX X .7-plzcnyl-3-(3,5-disulf0benzamido)-4- (4-ltydr xy-Z-penIadeCylpheuylazo) 5 p'yrazolone dipotassium salt To a solution of 5 grams of l-phenyl-3-(3,5-disulfozenzamido) 5-pyrazolone dipotassium salt (prepared according to the procedure given for Intermediate B, coupler XXXVI above using the appropriate intermediates) in 20 m1. of 50 percent pyridine was added at 20 C. a diazonium solution consisting of 3 grams of 4-amino-3- pentadecylphenol, 1.5 grams of isoamylnitrite and 2 grams of concentrated hydrochloric acid in 20 ml. of n-propyl alcohol. The resultant mixture was stirred at room temperature for 12 hours after which time it was poured into 100 ml. of saturated potassium chloride solution. The solid which separated was collected, and recrystallized from 50 ml. of 60 percent ethyl alcohol, yielding the product.

Couplers XL, XLI, XLII, XLIII and XLIV were each prepared according to the procedure given for coupler XXXIX above using the appropriate intermediates.

Coupler XLV: 1- [4- (3,5-dicarboxybenzamido)plzenyl] -3- ethox -4-(3-0ctadecylcarbamylphenylthio)-5-pyraz0l0/ze A mixture of 7.8 grams of Intermediate H below, 25 ml. of ethyl alcohol, 15 ml. of 2 N aqueous NaOH, and 35 ml. of water was stirred at 85 C. for 15 minutes. The solution was cooled to room temperature and acidified with 1:2 concentrated HClwater.

The solid which separated was filtered oil, washed with water, acetonitrile, and recrystallized from methanol, yielding 4 grams of product, MP. 200202 C.

Coupler XLV: Intermediate A.1-(4-nitr0phenyl)- 3-ethoxy-S-pyrazolone A mixture of 3l grams of 4-nitrophenylhydrazine, 100 ml. of ethyl alcohol, and 38 grams of ethyl-[3,B-dietl1oxyacrylate was refluxed for /2 hour. A solution of sodium ethoxi-de (prepared from 4.6 grams of sodium and 100 ml. of ethyl alcohol) was added and refluxed for another 20 minutes. This solution was acidified with glacial acetic acid and the solid which separate-d was filtered off, and recrystallized from 250 ml. of n-butyl alcohol, yielding 31 grams of product, M? l534 C.

Coupler XLV: Intermediate B.Z-(4-umirzoplzc'nyl)- 3-at]:0xy-5-pyruz0l0ne A mixture of 15 grams of Intermediate A above in ml. of ethyl alcohol was reduced using Pei/Charcoal at 50 p.s.i., hydrogen pressure.

The catalyst was filtered off and the solution poured into 500 ml. of water.

The product was filtered off and air dried, yielding 8.2 grams of product, M.P. l21-122 C.

Coupler XLV: Intermediate C.Triethyltrimesate Coupler XLV: Intermediate D.-Diethyl ester of trimesic acid, (3,5-dicarbethoxybenzoic acid) To a solution of 147 grams of the Intermediate C above in 2 liters of ethyl alcohol was added with stirring 250 ml. of 2 N NaOH in 500 ml. of ethyl alcohol. This mixture was refluxed for 30 minutes and stirred at room temperature for 12 hours, during which time a solid separated. This solid was filtered off and recrystallized from a mixture of 500 ml. of ethyl alcohol and 500 ml. of water, yielding 80 grams of product, M.P. 1535 C.

Coupler XLV: Intermediate E.-3,5-dicarbethoxybenzoyl chloride A mixture of 300 grams of Intermediate D above and 2 liters of thionyl chloride was refluxed for 2 hours, after which time it was concentrated in vacuo.

To the residue was added 250 ml. of dry benzene and again concentrated in vacuo.

. The acid chloride thus formed was used as such in pre' paring Intermediate F below.

Coupler XLV: Intermediate F.1-[4-(3,5-dicarbethoxybenzamido p'heny l] -3-etlz0xy-5-pyrazol0ne A mixture of 6.6 grams of Intermediate B above and 8.5 grams of Intermediate E above and 100 ml. of dry acetonitrile was refluxed for 5 hours. The mixture was cooled to room temperature and the solid was filtered off, dried, and recrystallized from glacial acetic acid, yielding 10 grams of product, M.P. 200201 C.

Coupler XLV: Intermediate G.3-octadecylcarbamylplzenylsulfenyl chloride Coupler X LV: Intermediate H .--I [4- (3,5 -dicarbethxybenzamido) phenyl] -3-ethoxy-4- (3 octadecy lcarbamylphenylthio -5-pyrazolone A mixture of Intermediate G above and 9.35 of Intermediate F in 200 ml. of dry dioxane was stirred at room temperature for 2 hours, heated to reflux for 1 hour, and concentrated in vacuo.

The residue was recrystalled from ethyl alcohol, yielding 8.5 grams of product, M.P. 1568 C.

Coupler XLVI: I-(4-sulf0phenyl)-3-(4-sulfoanilino)-4- (3-octadecylcarbamylphenylthio) 5 pyrazolone disodium salt A suspension of 25 grams of Intermediate B below in 100 ml. of ethyl alcohol and 200 ml. of 2 percent aqueous NaOH was stirred at room temperature for /2 hour, during which time all solid dissolved. The solution was cooled and acidified with 5 ml. of acetic acid and concentrated in vacuo.

The crude solid residue was recrystallized from methyl alcohol, yielding 10 grams of product, M.P. 2SO C.

Coupler XLVI: Intermediate A.-I-(4-flu0sulf0nylphenyl)-3-(4-fluolsulfonylanilino)-5-pyrazol0ne To 450 ml. of fluosulfonic acid at 5 C. was added with stirring grams of 1-phenyl-3-anilino-5-pyrazolone.

The resultant solution was stirred at 50 C. for 4 /2 hours, then poured onto 2 kg. of crushed ice. The solid was collected, washed with water, filtered, and dissolved in 2 liters of ethyl acetate. This solution was washed with 5 percent sodium bicarbonate solution, water, and saturated brine.

It was concentrated in vacuo and the residue was recrystallized from acetonitrile, yielding 36 grams of product, M.P. 290 C. decomp.

Coupler XLVI: Intermediate B.-1 (4 fluosulfonyl' phenyl) 3 (4-fluosulfanylanilino)-4--(3-octadecylcar bamylphenylthio)-5-pyrazolone A mixture of Intermediate G of Coupler XLV above (prepared from 24.5 grams of the disulfide) and 25 grams of Intermediate A above in 330 ml. of dry carbon tetrachloride was stirred at 55 C. for 12 hours.

The solution was then concentrated in vacuo and the residue was recrystallized from 300 ml. of ethyl acetate yiedling 25 grams of product, M.P. 209]l1 C.

Coupler XL VII: 4,4 (4 -octadecyloxybenzylidene) bas[1 phenyl 3 (3 ,5 -disul fobenzam ido) -5 -pyraz0lone] tetrapotassium salt To a refluxing solution of 5.2 grams of 1-pheny1-3- (3,5-disulfobenzamido)-5-pyrazolone dipotassium salt in 45 m1. of ethyl alcohol and 20 ml. of water was added a solution of 1.9 grams of Intermediate A below and 0.5 gram of piperidine in 35 ml. of ethyl alcohol. The solution was refluxed for /2 hour and cooled to room temperature. The solid which separated was collected, recrystallized from percent ethyl alcohol, yielding 5 grams of product.

Coupler XLVII: Intermediate A.4- octadecyloxybenzaldelzyde To a solution of 23 grams of sodium metal and 122 grams of 4-hydroxybenzaldehyde in 500 ml. of ethyl alcohol was added 333 grams of l-bromoctadecane. The mixture was refluxed with stirring for 20 hours during which time a solid separated. This solid was filtered and the filtrate was concentrated in vacuo. The residual material was then distilled at 253 C. at 1 mm. pressure yielding 250 grams of product.

Coupler XLVII. O6-Bt2IlZ0yl-1Z- (4 hydroxy-Z-pentadecylphenylazo)-4-(3-sulfobenzamido) acetanilide sodium salt To a solution of 4.5 grams of a-benzoyl-4-(3-chlorosulfonylbenzamido) acetanilide in 12 ml. of 90 percent pyridine was added at 20 C. a diazonium mixture consisting of 3.2 grams of 4-amino-3-pentadecylphenol, 1.4 grams of isoamylnitrite and 2 ml. of concentrated hydrochloric acid in 20 ml. of n-propyl alcohol. The resultant solution was stirred at room temperature for 12 hours after which time it was poured into 50 ml. of saturated sodium chloride solution. The yellow solid which separated was collected, and recrystallized twice from ethyl alcohol, yielding 2.2 grams of product.

Coupler XLIX was prepared according to the procedure given for coupler XLVIII above using the appropriate intermediates.

Coupler LI: vt-Benzoyl-a-(3-0ctadecylcarbamylphenylthio)-3,5-dicarboxyacetanilide To a mixture of 7 grams of Intermediate A below in ml. of dioxane at 50 C. was added a solution of 3-octadecylcarbamylphenylsulfenyl chloride (Intermediate G of coupler XLV above, prepared from 8.1 grams of the disulfide), in 100 ml. of dioxane. This mixture was stirred for 12 hours after which time the solution was concentrated in vacuo. A solution of the gummy residue in 100 ml. of ethyl alcohol and 13 ml. of 2 N aqueous sodium hydroxide was heated at 40 C. for 1 hour after which time it was acidified with concentrated hydrochloric acid. The solid which separated was collected and re crystallize-d twice from ethyl alcohol, yielding 2 grams of product, M.P. 140l42 C.

Coupler LI: Intermediate A.a-Benzyl-3,5- dical'bomethoxyacetanilia'e To a refluxing mixture of 102 grams of ethyl a-benzoylacetate and grams of sodium acetate in 100 ml. of xylene was added 105 grams of dimethyl S-aminoisophthalate. The resulting solution was refluxed under a steam condenser for 3 hours after which time it was concentrated to /2 the original valume and cooled to room temperature. The solid which separated was collected and recrystallized from methyl alcohol, yielding 40 grams of product, M.P. 165167 C.

The following examples illustrate typical embodiments of the invention.

Example 1 A color film having the structure substantially as shown in FIG. 1 was prepared by coating a subbed cellulose acetate film support successively with the following layers which correspond to the numbered layers in FIG. 1.

Layer 1I.-A gelatino silver chloride emulsion coated at 40 mg. silver per square foot and 100 mg. gelatin per square foot and containing 2.7 gm. zinc sulfide (nuclei) per square foot, 50 mg. 1-hydroxy-4-(3-octadecylcarbamylphenylthio) N ethyl-3,5'-dicarb0xy-2- naphthanilide per square foot and mg. 2-octadecyl-5- sulfohydroquinone potassium salt per square foot. The phenolic DDR coupler of this layer yields a ditfusible indoaniline cyan dye image upon reaction with oxidized color developing agent in the uninhibited areas of layer 11.

Layer 12.-A red-sensitive gelatino-silver bromoiodide emulsion coated at 75 mg. silver per square foot and 100 mg. gelatin per square foot and containing 60 mg. of the DIR compound, 2-{4-[3-(4-tert-amyl x sultophenoxy) benzamido]phenethyl}-x-(l-phenyl-S-tetrazolythio) hydroquinone (Compound I), per square foot. The DIR compound of this layer and of layers 15 and 18, cross oxidizes with oxidized color developing agent, in the region of exposure, to form a quinone which compound releases the tetrazolylthio radical to yield the corresponding mercaptan which is effective to inhibit the development of the adjacent nucleated silver halide of layers 11, 14 and 17 respectively.

Layer 13.-A gelatino-silver iodide emulsion coated at 50 mg. silver per square foot and 100 mg. gelatin per square foot and containing 30 mg. of the nondifiusing magenta colored filter dye, 1-hydroxy-4-(4-tert-butylphenoxy)-4-phenylazo-2-naphthamide, per square foot and 30 mg. 2-octadecyl-S-sulfo-hydroquinone potassium salt per square foot. The silver iodide of this layer and of layer 16 serves to prevent upward diffusion of the mercaptan from layers 12 and 15.

Layer 14.-A gelatino-silver chloride emulsion coated at 40 mg. silver per square foot and 100 mg. gelatin per square foot and containing 5.5 X10" gm. zinc sulfide (nuclei) per square foot, 50 mg. of 1-phenyl-3-(3,5- dissulfobenzamido) 4-(2-hydroxy-4-n-pentadecylphenylazo)-5-pyrozolone dipotassium salt per square foot and 15 mg. 2-octadecyl-5-sulfo-hydroquinone potassium salt per square foot. This 5-pyrazolone DDR coupler yields a ditfusible magenta azomethine dye image in the process.

Layer I5.-A green-sensitive gelatino-silver bromoiodide emulsion coated at 0.075 grams silver per square foot, 100 mg. gelatin per square foot, and 60 mg. of DIR compound, 2-{4- [3 (4-t-amyl-x-sulfophenoxy benzamido] phenethyl} x (1-phenyl-5-tetrazolylthio)hydroquinone (Compound I), per square foot.

Layer 16.A gelatino-silver iodide emulsion containing 50 mg. silver per square foot and 100 mg. gelatin per square foot and also 66 mg. 1-(2,4,6-trichlorophenyl)- 3 {3 [a (2,4-di tert amylphenoxy)acetamido]benzamido}-4- (p-methoxyphenylazo -5-pyrazolone per square foot and 30 mg. 2-octadecyl-5-sulfohydroquinone potassium salt per square foot. The yellow pyrazolone coupler of this layer serves as a light filter to confine the blue image exposure to layer 18.

Layer 17.A gelatino-silver chloride emulsion coated at 50 mg. silver per square foot and 100 mg. gelatin per square foot and containing also 1.1 10 gm. zinc sulfide (nuclei) per square foot, 100 mg. a-benzoyl-a-(3- octadecylcarbamylphenylthio) 3,5 dicarboxyacetanilide per square foot and 15 mg. 2octadecyl-S-sulfo-hydroquinone potassium salt per square foot. The DDR coupler of this layer yields a dilfusible yellow azo methine dye image in the process.

Layer 18.A blue-sensitive gelatino-silver bromoiodide emulsion coated at 0.075 gram silver per square foot and 100 mg. gelatin per square foot and containing in addition, 30 mg. of the DIR compound, 2-{4-[3-(4-tertamyl x sulfop'nenoxy)benzamido]phenethyl} x (1- phenyl-S-tetrazolylthio)hydroquinone (Compound I), per square foot.

The resulting element was exposed to a colored subject and immersed with a paper receiving sheet having a gelatin layer containing a mordant such as cetyl trimethyl ammonium bromide in the following color developing solution and pressed for about 5 minutes at F. into contact with the paper reception sheet.

Ascorbic acid rng 200.0 4-amino-N-ethyl-N-/3-hydroxyethyl aniline sulfate g 4.0 4-arnino-N-ethyl-N-B-methylsulfonamido-ethyl- 2-methyl aniline sulfate g 1.0 Na CO -H O g 40.0 Aminoethanol ml 2.2 Potassium bromide rng 500.0

v Sodium thiosulfate (pentahydrate) mg 200.0

6-nitrobenzimidazole nitrate mg 5.0

H 0 to 1 liter pH 11.0 (adjusted).

As a result, the exposed silver halide in layers 12, 15 and 19 develops and the DIR compound therein crossoxidizes with oxidized color developing agent obtaining in the reaction thereby releasing a development inhibiting mercaptan that inhibits development of adjacent areas of the nucleated emulsion layers 11, 14 and 17 respectively. The residual developer solution migrates to the positive areas of layers 11, 14- and 17%, causing physical development to proceed and difliusible cyan, magenta and yellow dyes to be produced which transfer by diffu" sion imagewise and in register to the mordanted receiving sheet to provide a multicolor positive reproduction of the original subject.

Example 2 A color film having the structure substantially as shown in FIG. 1 was prepared by coating on a celulose acetate film support successively with the following layers which correspond to the numbered layers in FIG. 1:

Layer 11.-A gel-atino-silver thiocyanate emulsion coated at 30 mg. silver per square foot and mg. gelatin per square foot and containing 2.7 10 grams zinc sulfide (nuclei) per square foot, 50 mg. l-hydroxy- 4-(3-n-octadecylcarbamyl-phenylthio) N ethyl 3,5- dicarboxy-Z-naphthamide per square foot and 15 mg. 2 octadecyl 5 sulfohydroquinone potassium salt per square foot. The phenolic DDR coupler of this layer yields a dififusible indoaniline cyan dye image upon reac- 37 tion with the oxidized color developing agent in the unhibited areas of layer 11.

Layer 12.A red-sensitive gelatino-silver bromoiodide emulsion coated at 0.112 grams silver per square foot and 160 mg. gelatin per square foot and containing 45 mg. of the DIR compound, 2-{4-[3-(4-tert-amyl-xsulfophenoxy)benzamido] phenethyl}-x-(1 phenyl-S-thiazolylthio)hydroquinone (Compound I), per square foot.

The DIR compound of this layer, and of layers 15 and 18, cross oxidizes with oxidized color developing agent, in the region of exposure, to release the tetrazolylthio radical which is eflFective to inhibit the development of the adjacent nucleated silver salt of layers 11, 14 and 17 respectively.

Layer 13.-A gelatino-silver iodide emulsion coated at 50 mg. silver per square foot and 80 mg. gelatin per square foot and containing 22.5 mg. of the nondifiusing magenta colored filter dye, 1-hydroxy-4-(4-tert-butylphenoxy)-4-phenylazo-Z-naphthamide, per square foot and 30 mg. 2-octadecyl-5sulfohydroquinone potassium salt per square foot. The silver iodide of this layer and of layer 16 serves to prevent upward diffusion of the mercaptan from layers 12 and 15.

Layer 14. A gelatino-silver thiocyanate emulsion coated at 49 mg. silver per square foot and 100 mg. gelatin per square foot and containing 5.4x 10 gm. zinc sulfide (nuclei) per square foot, 50 mg. of l-phenyl-3- (3,5disulfobenzamido)-4-(2-hydroxy 4 n pentadecylphenylazo)-5-pyrazolone dipotassium salt per square foot and 15 mg. 2-octadecyl-5-sulfohydroquinone potassium salt per square foot. This 5-pyrazolone DDR coupler yields a diifusible magenta azomethine dye image in the process.

Layer 15.-A green-sensitive gelatino-silver bromoiodide emulsion coated at 0.075 grams silver per square foot, 100 mg. gelatin per square foot, and 30 mg. of the DIR compound, 2-{4-[4-tert-amyl-x-sulfophenoxy) benzamido]phenethyl}-x-(1-phenyl 5 tetrazolylthio) hydroquinone, per square foot.

Layer 16.A gelatino-silver iodide emulsion containing 50 mg. silver per square foot and 100 mg. gelatin per square foot and 100 mg. gelatin per square foot and also 66 mg. 1 (2,4,6 trichlorophenyl)-3-{3-[a-(2,4-di-tertamylphenoxy)acetamidoJbenzamido} 4 (p methoxyphenylazo)-5-p yrazolone per square foot and 30 mg. 2 octadecyl 5 sulfohydroquinone potassium salt per square foot. The yellow pyrazolone coupler of this layer serves as a light filter to confine the blue image exposure to layer 18.

Layer J7.A gelatino-silver thiocyanate emulsion coated at 40 mg. silver per square foot and 100 mg. gelatin per square foot and containing also 7.2 grams zinc sulfide (nuclei) per square foot, 100 mg. a-benzoyl-a-(3-octadecylcarbamyl phenylthio-3,5-dicarboxyacetanilide per square foot and mg. 2-oct adecyl- 5-sulfohydroquinone potassium salt per square foot. The DDR coupler of this layer yields a diifusibleyellow azomethine dye image in the process.

Layer 18.-A blue-sensitive gelatino-silver bromoiodide emulsion coated at 75 mg. silver per square foot and 100 mg. gelatin per square foot and containing, in addition, 30 mg. of the DIR compound, 2-{4-[3-(4-tert-amylx-sulfophenoxy)benzamido1phenethyl} x (l-phenyl-S- tetrazolylthio)hydroquinone, per square foot.

The resulting element was exposed to a colored subject and immersed with a paper receiving sheet having a gelatin layer containing a mord-ant such as cetyl trimethyl ammonium bromide in the following color developing solution and placed for about 5 minutes at 85 F. into contact with the paper reception sheet.

Ascorbic acid mg 200 4-amino-N-ethyl-N- 8-hydroxyethyl aniline sulfate g 5 N21 CO H O g 40 foot and 214 mg. of

H O to 1 liter pH 11.0 (adjusted).

As a result, the exposed silver halide in layers 12, 15 and 18 develops and the DIR compound therein crossoxidizes with the oxidized color developing agent obtained in the reaction thereby releasing the development inhibiting mercaptan that inhibits development of adjacent areas of the nucleated silver thiocyanate emulsion layers 11, 14 and 17 respectively. The residual developer solution migrates to the positive areas of layers 11, 14 and 17 causing physical development to proceed and diifusible cyan, magenta and yellow dyes to be produced which transfer by diffusion imagewise and in register to the mordanted receiving sheet to provide a multicolor positive reproduction of the original subject thereon.

Example 3 A color film having the structure substantially as shown in FIG. 2 was prepared by coating a subbed cellulose acetate film support successively with the following layers which correspond to the numbered layers of FIG. 2:

Layer 21.-A fogged gelatino-silver chlorobromoiodide emulsion containing one mole of silver, 8,400 cc. of 1 percent aqueous solution of the magueta-forming DDR coupier, 1 phenyl-3-(3-5-disulfobenzamido)-4-(4-octadecyloxyphenylazo)-5-pyrazolone disodium salt, 740 cc. of 7.5 percent saponin in water, 134 cc. of 2.7 percent mucochloric acid in water and water to make 22,100 grams was coated on the support so that the resulting layer contained 30 mg. of silver per square foot, 30 mg. of the DDR coupler per square foot and 184 mg. of gelatin per square foot.

Layer 22.-A gelatino-silver chlorobromoiodide emulsion sensitized to green light and containing one mole of the silver halide, the DIR compound, 2-[4-(3,5-clisulfobenzamido)phenethyl] x (1-phenyl-5-tetrazolylthio)hydroquinone Disodiurn Salt Dihydrate (Compound V), dispersed in aqueous gelatin solution, 400 cc. of 7.5 percent saponin, 73 cc. of 2.7 percent mucochloric acid and water to make 12,000 grams was coated to give 62 mg. of silver per square foot, 91 mg. of the DIR compound per square gelatin per square foot.

Layer 23.-A gelatino-silver chloride emulsion containing one mole of silver, 2.6 cc. of 7.5 percent saponin, 43 cc. of 2.7 percent mucochloric acid and water to make 6,480 grams was coated in a layer having mg. of silver per square foot and 200 mg. of gelatin per square foot.

Layer 24.-This layer is substantially the same as layer 21 except that the fogged silver halide emulsion contained the cyan-forming DDR coupler, 2 (3,5 -disulfobenzamido)-5-methyl-4 (4-octadecyloxyphenylazo) phenol dipotassium salt, in lieu of the magneta-iormiug DDR coupler, the coupler being coated to obtain a layer having 87 mg. of the coupler per square foot.

Layer 25.This layer is substantially the same as layer 22 except that one mole of a gelatino-silver chlorobromide emulsion sensitive to red light was utilized in lieu of the green-sensitive silver halide emulsion.

Layer 26.This layer is substantially the same as layer 23 except that sufiicient Carey Lea silver is added to obtain a coverage of 4.6 mg. per square foot.

Layer 27 .-This layer is substantially the same as layer 21 except that the fogged silver halide emulsion containing the yellow-forming DDR coupler, 1-hydroxy-4-(2,4- dinitrophenylthio) N [5-(2,4-di-tert-amylphenoxy)butyIJ-Z-naphthamide, was used in lieu of the magenta-forming DDR coupler.

Layer 28.This layer is substantially the same as layer 22 except that one mole of gelatino-silver chlorobromide emulsion sensitive to blue light was used in lieu of the green-sensitive silver halide emulsion.

Layer 29.-This is a protective gelatin layer at a coverage of 50 mg. of gelatin per square foot.

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Classifications
U.S. Classification430/214, 430/240, 430/443, 430/202, 430/219, 430/217, 430/505, 430/957
International ClassificationC07D231/52, C09B31/078, C07D257/04, C09B43/124, C09B39/00, C07D231/32, C09B35/04, G03C8/08, C07C47/575, G03C7/30, C07D263/58, C09B43/08, C07C45/70, C07F3/12, G03C5/50, C07D231/28, C07D231/26
Cooperative ClassificationG03C5/50, G03C7/3003, C07D231/32, C09B39/00, C07C47/575, C09B43/124, G03C8/08, C07D231/26, Y10S430/158, C07D231/28, C09B35/04, C09B43/08, C07D263/58, C07C45/70, C07D257/04, C07F3/12, C07D231/52, G03C7/30541, C09B31/078
European ClassificationC07C45/70, C07D231/28, G03C7/30C, G03C5/50, C09B43/124, C09B31/078, C07F3/12, C07D231/32, C07C47/575, C09B39/00, G03C8/08, C07D231/52, C09B35/04, C07D231/26, C09B43/08, C07D263/58, C07D257/04