US3287133A - Photographic dye developer dispersions utilizing water-soluble sulfites - Google Patents

Description

Nov. 22,

PHOTOGRAPHIC DYE.

ING

WATER-SOLUBLE SULFITES Filed March 1, 1963 ifllm'l'l'ml l/SUPPORT MORDANT LAYER POD CON'IHINING PROCESSING MATERIAL PROTECTIVE LAYER B LUE-S ENSITIVE EMULSION LAYER YELLOW DYE DEVELOPER LAYER NTERLAYER /GREEN-SENS|TNE EMULSION LAYER MAGENTA DYE DEVELOPER LAYER INTERLAYER /REQsENs|T|vE EMULSION LAYER CYAN DYE DEVELOPER LAYER S UPPORT Carl llm'lliamgJr:

INVENTOR.

yzuzw United States Patent of New Jersey Filed Mar. 1, 1963, Ser. No. 262,167 16 Claims. (Cl. 96-77) The present invention concerns photographic materials, and more particularly, photographic dye developers.

Compounds which contain in the same molecule both the chromophoric system of a dye and a photographic silver halide developing moiety have been described in the photographic art as useful compounds in photographic elements for preparing colorimages by diffusion transfer processes. Such compounds are commonly called dye developers. Photographic elements containing such dye developers generally comprise a plurality of photosensitive silver halide emulsions Wherein each of theemulsions is selectively sensitized to a different region of the spectrum. A dye developer is positioned contiguous to the silver halide in each of such emulsions. Such a photoelement is processed with an alkaline solution and the latent image is developed in the negative image areas with the dye developers, this development immobilizing the dye developers in such negative image areas, and the dye developers in the unexposed areas diffuse to the surface imagewise and are mordanted in a receiving sheet to form a positive color image. Such color diffusion transfer processes are disclosed in US. Patents 2,559,643, 2,647,- 049, 2,698,798, 2,774,668 and 2,983,606, as well as elsewhere in the literature.

A particularly useful method for incorporating dye developers into compositions used for coating layers on photographic elements is to dissolve the dye developer in a high-boiling water-immiscible organic solvent and to disperse the organic solvent in finely-divided droplets in a hydrophilic organic photographic vehicle or substrate such as gelatin. Such dispersions of dye developer in highboiling solvents are known in the art and can be used to prepare particularly uniform distributions of the dye developer in the photographic element. The use of such dispersions of dye developers in photographic elements is disclosed in Belgian Patent 607,420 granted August 15, 1961, copending Weyerts application, U.S. Serial No. 50,932 filed August 22, 1960, now abandoned and US. Patent 2,983,606.

However, one of the practical problems in manufacturing photographic elements having coated thereon dispersions of dye developers is that such dispersions readily crystallize or agglomerate unless coated shortly after preparation. As is the case in the coating of many photographic compositions on a commercial scale, it is oftentimes desirable or necessary to store or delay the coating of a given composition for substantial periods after its preparation.

It is accordingly an object of the invention to provide novel dispersions of photographic dye developers that can be stored for substantial periods without crystallization or agglomeration of the dye developers in the dispersions.

It is another object of the invention to provide a novel process for treating photographic dye developer disper- SlOIlS.

These and other objects of the invention will be apparent from the descriptions of the invention and the claims hereafter.

The present invention concerns photographic hydrophilic organic colloids containing substantially uniformly dispersed therein finely-divided droplets of water-immiscible organic solvents containing dissolved therein dye developers that have been treated with water-soluble sulfites.

Dispersions of dye developers can be prepared by dissolving the dye developers in a high-boiling solvent and thereafter dispersing the resulting solution in a hydrophilic organic colloid. Generally, water-soluble or low boiling solvents are used with the high-boiling solvent as auxiliary solvents.

The present sulfite treatment for dye developer dispersions can be efiected by the addition of a water-soluble sulfite to any stage in the preparation of the subject dye developer dispersions and intimately associating or contacting the dye developer and the water-soluble sulfite. For example, the water-soluble sulfite can be added with the dye developer in the hydrophilic organic colloid during the preparation of such dispersions, after the preparation of the dispersions as a final aqueous washing or treating bath, to the dye developer dispersions after their preparation, or at more than one of such stages. The amount of water-soluble sulfite used in preparing the dye developer dispersions can be widely varied, although concentrations of water-soluble sulfite utilized generally range from about .001 to .65 mole of water-soluble sulfite for each mole of dye developer. Suitable water-soluble sulfites include such inorganic sulfite salts as ammonium sulfite and alkali metal sulfites such as sodium and potassium sulfite.

Hydrophilic organic colloids containing dispersed therein dye developers in high-boiling solvents treated with water-soluble sulfites as described above manifest a substantial decrease in the tendency of the dye developers to crystallize or agglomerate. Such emulsions or photographic coating materials can be stored for substantial periods prior to coating without deleterious eifect on the properties of the properties of the emulsion.

Dye developers are well known in the photographic art. Such compounds function both as a silver halide developing agent and as a dye in photographic diffusion transfer systems. Dye developers are characterized as being relatively nondiffusible in colloid layers such as the hydrophilic organic colloids used in photographic emulsions at neutral pH, but difiusible in the photographic elements in the presence of alkaline processing solutions. Generally, such dye developers are insoluble in water, per se, which property usually necessitates the use of organic solvents to incorporate the dye developers into the organic colloid layers of the photoelements. The dye developers are particularly characterized as containing both a chromophoric or dye moiety and at least one moiety having a silver halide developing agent function. The invention is particularly useful in preparing dispersions of dye developers wherein the chromophoric moiety is an azo or anthraquinone dye moiety and the silver halide developing moiety is a benzenoid moiety such as a hydroquinonyl moiety.

Representative dye developers of use in the dispersions of the invention have the general formula MN=ND in which M is an aromatic or heterocyclic ring or ring system such as a benzene, naphthalene, tetralin, anthracene, anthraquinone, pyrazole, quinoline, etc., ring which can be substituted with such groups as hydroxyl amino, keto, nitro, alkoxy, aryloxy, acyl, alkylamido, arylamido, alkyl aryl, carboxamido, sulfonamido, carboxyl or sulfo groups. D represents a silver halide developing agent moiety imparting the developing agent function to the dye developer such as a hydroquinolyl group which can be substituted with amino, alkylarnino, alkyl, hydroxyl, alkoxyl or halogen groups.

A useful class of dye developers is disclosed in Australian Patent 220,276 accepted December 17, 1958, and

3 German Patent 1,036,640, August 14, 1958, and have the general formulas YRArN=N Q i: )m P and wherein R is an alkylene group preferably of from 1 to carbon atoms; Ar is an aryl group of the benzene or naphthalene series; each Z is a lower alkyl group having 1 to 5 carbon atoms and preferably methyl or ethyl, or halogen, e.g., chlorine; Z is a lower alkoxyl group having 1 to 5 carbon atoms and preferably methoxy or eth- 'oxy, halogen or a lower alkyl group having 1 to5 carbon atoms; In is an integer of 0, 1 or 2; A is an integer of l or 2; Y is a 2,5- or 2,3- or 3,4-dihydroxypheny1 group which can be substituted by alkyl or halogen groups; Q is the residue of a photographic color coupling component such as a phenol, naphthol, S-pyrazolone or openchain reaction methylene coupler containing the group -CO--CH -CO--, for example:

4-[p-(2',5-dihydroxyphenyl)-phenylazo]-5-acetamido-1- naphthol,

, 4- [p-(2',5 '-dihydroxyphenethyl) -phenylazo] -5-benzamido-l-naphthol,

1-phenyl-3-methyl-4-[p-(2',5-dihydroxyphenethyl)- phenylazo] -5-pyrazolone,

'2- [p- (2'-5-dihydroxyphenethyl) -phenylazo] -4-acetamidol-naphthol, 2- [p-(2,5-dihydroxyphenethyl)-phenylazo] -4-amino-1- naphthol I OCH;

(magenta dye developer) I 2- [p- 2',5'-dihydroxyphenethyl) -phenylazo] -4-methoxyl-naphthol,

2- [p- (2,5'-dihydroxyphenethyl) -phenylazo-4-ethoxy- I- naphthol,

2- [p-( 2',5-dihydroxyphenethyl) -phenylazo] -4-n-propoxyl-naphthol,

2- [p- (2',5 '-dihydroxyphenethyl -phenylazo] -4-iso-propoxyl-naphthol 1- 4-(2,5 '-dihydroxyphenylpropyl) -phenyl] -3-p.- 'yhydroxypropyl-carbonamido -4-mesitylazo-5- pyrazolone (yellow),

l- [4- 2',5 '-dihydroxyphenylpropyl -phenyl] -3- [N- (nhexyl)carbonamido1-4-[3'-(2",5"-dihydroxyphenyl) 1- [4'-hydroquinonylethyl] -phenyl-3-ethyl-carboxamido- 4- (2",4",6"-trimethyl) -phenylazo-5-pyrazolone (yellow) 1- [p- 2,S-dihydroxyphenylpropyl -phenyl] -3-(N-ethyl carboxamido -4- 2,4,6-trimethylphenylazo -5-pyrazolone (yellow),

1-phenyl-3-N-n-butyl-carb oxamido-4- [p- (2,5 '-dihydroxyphenethyl -phenylazo] -5-pyrazo1one,

1-phenyl-3 -N-n-heXylcarboXamido-4- [p- (2',5'-dihydroxyphenethyl -phenylazo] -5-pyrazolone,

1-phenyl-3-carbethoxy-4- [p- (2',5-dihydroxyphenethyl) phenylazo] -5-pyrazolone,

2- p- (2',5 '-dihydroxyphenethyl) -phenylazo] -4-isopropoxyl-naphthol,

l-phenyl-3 -N-cyclohexylcarboxamido-4- [p- (2',5'-dihydroxyphenethyl) -phenylazo] -5-pyrazolone,

1-phenyl-3-phenyl-4- [p(2',5'-dihydroxyphenethyl) phenylazo] -5 -pyrazolone,

1-phenyl-3-amino-4-{4'- [p- 2",5"-dihydroxyphenethyl) phenylazo] -2,5-diethoxyphenylazo}-5-pyrazolone,

I-acetoxy-Z- [p- (B-hydroquinonylethyl) -phenylazo] -4- a methoxy naphthalene,

4-isobutoXy-2- [p- (fi-hydroquinonylethyl) -phenylazo] -1- naphthol,

l-acetoxy-Z- [p- (B-hydroquinonylethyl) -phenylazo] -4- propoxy naphthalene,

2- [p- (2',5 -dihydroxy-4'-methylphenethyl) phenylazo] -4- pr'opoxy-l-naphthol,

British Patent 804,973, November 26, 1958, and have the general formulas wherein A represents an anthraquinone nucleus, Drepresents an organic radical having a developing function and containing an aryl nucleus such as benzene or naph-,

thalene nuclei, substituted by at least two substituents selected from hydroxyl, amino and substituted amino groups so that the resulting compound is capable of developing exposed silver halide, Q represents a hydrogen atom or an alkyl group or, when the substituents on the aryl nucleus of D are hydroxyl groups, Q can also be an acyl group, which can be aliphatic, (e.g., acetyl) or aromatic (e.g., benzoyl), Z is a bivalent organic radical containing at least one methylene (CH group, m is an integer of 1 to 4 and each Ycan be a hydrogen or halogen atom or an amino, alkyl, aryl, nitro, alkylamino, arylamino, aryloxy, alkoxy, hydroxyl, sulphonamido, carboxamido, carboxy, sulpho,

group. Examples of these dye developers are:

I 1,4-bis (2',5 '-dihydroxyanilino) -anthraquinone, 1,5-bis(2,5 '-dihydroxyanilino)-4,8-dihydroxy-anthraquinone,

1,4-bis [,3- (3 ,4'- dihydroxyphenyl) -ethylamino1-anthraquinone OH 3 R IIIHCH- IHF 1 1 I l y OH (')H I I NHCH-OH' (cyan dye developer) 1,4-bis 8- (2',5'-dihydroxyphenyl) -isopropylamino] anthra quinone,

1,4-bis [,3- (2',5 -dihydroxyphenyl) -ethylamino] anthraquinone,

1 -chloro-4- [fi- 2',5 -dihydroxyphenyl -ethylarnino] anthraquinone,

N-monobenzoyl- 1,4-bis [fi- (3 ,4'-dihydroxyphenyl) ethylamino] anthraquinone,

N-rnonobenzoyll ,4-bis [fi-(2,5-dihydroxyphenyl) -ethylamino] anthraquinone,

,8-dihydroxyl ,4-bis fi-hydro quinonyl-u-methyl) ethylamino] anthraquinone,

1,4-bis (fl-hydroquinonyl-a-ethyl) ethylamino] -anthraquinone,

5 -hy droxy-l ,4-bis fi-hydroquinonyl-a-methyl) -ethylamino] anthraquinone,

1- B-hydroxy-a-ethyl-ethylamino) -4- (B-hydroquinonyla-methylethyl amino-anthraquinone,

1- (butanol-2-arnino -5 ,8-dihydroxy-4-hydroquinonylisopropylarnino-anthraquinone,

1,4-diamino-2- [e- (2',5-dihyd.roxyhydrocinnamido) -pentoxy] -anthraquinone (magenta),

1,4-diamino-2- [ea-methyl-2',5 '-dihydroxyhydrocinnamido) -pentoxy] -anthraquinone (magenta) and 1 ,4-diarnin 0-2- e- (a-ethyl-2,5 -dihydroxyhy drocinnamido -pentoxy] -anthraquinone (magenta) t I-|TH on AA 0 (CHmNHC 0 mens- W 02115 0 NH: on

In Formula 1 above the expression bivalent organic radical Z refers to organic radicals having the two free valences attached to difierent atoms. As examples of such suitable bivalent organic radicals, mention may be made of alkylene radicals such as CH CH CH 5 --CHz-CH- as Well as bivalent radicals such as It is also intended that Z can be saturated, unsaturated, such as CH --CH:CH-CH or substituted, such as chloroalkylene or hydroxyalkylene. Where Z is an alkylene group, best results are obtained by the use of a lower alkylene group, e.g., an alkylene group, containing 1 to 5 carbon atoms, and preferably an ethylene group.

Acylation of amino-nitrogen atoms which are part of the chromophoric system of dye developers has the effect of shifting the visible absorption band of the compound toward higher frequencies (shorter wavelengths). Thus, acylating one amino-nitrogen of the cyan, 1,4-bis- 6 [,8-(2',5'-dihydroxyphenyl)-ethylamino] anthraquinone changes its color to a magenta, and acylating both the amino-nitrogen atoms changes its color to an orangeyellow. Similarly the acylation of hydroxyl groups of the above-described types of dye developers can be expected to shift the color of the dye developers. Thus, the dye developers can undergo a change in structure and/or color during the development reaction, for example through hydrolysis, and the dye which is transferred may have a color different than that of the dye developer originally present in the sensitive element.

Additional suitable dye developers are disclosed in Belgian Patent 554,935, British Patents 804,971, 804,973- 5 and French Patent No. 1,168,292.

The following dye developers are also useful in preparing the dispersions of the invention:

Cyanurated dye developers such as Z-hydroquinoneamino-4-(p-phenylazo)anilino-6-hydroxy-4 triazine described in Canadian Patent 579,038. Anthraquinone dye developers such as 1,4-bis(2',5'-dihydroxyanilino)-anthraquinone and 1,4-diamino-N-(B-2,5'-dihydroxyphenyl-amethyl-ethyl)2,3 anthraquinonedicarboximide. Amino substituted anthraquinone dye developers such as prepared by reaction of 1-amino-4-(p-aminoanilino)-anthraquinone-Z-sodiurn sulfonate with chloroacetamido hydroquinone monobenzoate. Dye developers obtained by reaction of 1-phenyl-3-amino-4-phenylazo-5-pyrazolone or 1,4-bis(fi-aminoethylamino)-anthraquinone with homogentisic acid lactone or acid chloride, or gentisic acid chloride, e.g., 1-phenyl-3-(2',5'-dihydroxyphenylacetamido)-4-phenylazo-S-pyrazolone described in Canadian Patent 577,021 dated June 2, 1959. Naphthamide dye developer such as 1-(2,5-dimethoxyphenylazo)-2- hydroxy-N-(2',5'-dihydroxyphenyl)-3 naphthamide described in French Patent 1,168,292 dated August 25, 1958. Diazo dye developers such as 2-[p-(1-hydroxy-3, 6-disulfo-8-amino-2 naphthylazo) 3,3 dimethoxybisphenyleneazo]-hydroquinone and 2-(2',5'-dimethoxy-4- [p (2,5" dihydroxyphenethyl)phenylazo] phenylazo)-1,8-naphthalene diol-3,6-disulfonic acid. Arylazonaphthol dye developers, e.g., 1-amino-4-phenylazo- Z-naphthol. Anthrapyridone dye developers, e.g., 1- acetyl 3 ,3 (2,5 dihydroxyphenyl) ethyl 6 )3- (2,5' dihydroxyphenyl) ethylaminoanthrapyridone. Thiohydroquinoly dye developers, e.g., 1-phenyl-3- methyl 4 [p (2',5' dihydroxyphenylthioethyl)- phenylazo1-5-pyrazolone described in Belgian Patent 5 68,- 344. Ortho coupled dye developers exhibiting limited sensitivity to changes of pH, e.g., 2-[p-(2,5"-dihydroxyphenoxy)phenylazo] 4 methoxy 1 naphthol and 1 phenyl 3 methyl 4 [p hydroquinolylsulfonyl)- phenylazo]-5-pyrazolone. Oxalyl ester dye developers, e.g., 1 phenyl 3 amino 4 [p (2',5' bisethoxalyloxyphenethyl)-phenylazo]-5-pyrazolone. Leuco compounds can also be used similarly, e.g., 1-phenyl-3- methyl 4 (2' methyl 4 diethylamino)anilino 5- pyrazolone, which do not exert a filtering action on underlying emulsion'layers and which are immobilized in the developed regions, difiuse imagewise from undeveloped areas to the reception layer and are oxidized to colored images therein.

In preparing the subject dispersions of dye developers at high-boiling solvent or carrier for the dye developers is utilized. Suitable high-boiling and water-immiscible organic liquids have a boiling point above about C. The high-boiling solvent can be used alone in dissolving the dye developer and in forming the dispersion or can be mixed with a low-boiling organic solvent (e.g., boiling at least 25 C. below the boiling point of the higher boiling solvent), or a water-soluble organic solvent, as an auxiliary solvent to facilitate solution of the dye developer. A preferred range of proportions of high-boiling solvent to auxiliary are 1/0 to 1/10 on a weight basis. Such auxiliary solvents can be readily removed from the high-boiling solvent, for example, by

cellulose acetate, etc.

are preferably utilized.

7 air-drying a chilled, noodled dispersion or by continuous water washing.

Typical high-boiling, water-insoluble solvents that can be used to dissolve dye developers in preparing the dis-- persions of the invention are described on page 2, col. 2 and page 3, col. 1 of US. Patent 2,322,027 can be used. Such classes of solvents as organic carboxylic acid esters, organic phosphate esters, N-lower alkyl acetanilides, N,N-

di-(lower. alkyl)alkylamides and the like are typically employed.

The following are representative substantially waterinsoluble organic solvents for use alone, or in combination with the auxiliary solvents, in the preparation of the dye developer dispersions which can be treated with the water-soluble sulfites in accordance with the invention:

Benzyl phthalates, ditetrahydrofurfuryl phthalate, ,8-

methoxyethyl phthalate, ethyl N,N-di-n-butylcarbamate,

guaiacol acetate (o-methoxyphenyl acetate), tetrahydrofurfuryl propionate, ethyl benzyl malonate, triethyl citrate acetyl, triethyl citrate, tetrahydrofurfuryl succinate,

tricresyl phosphate, tri-p-tert, butylphenyl phosphate, triphenylphosphate, ditetrahydrofurfuryl succinate, ditetrahydrofurfuryl adipate, tetrahydrofurfuryl benzoate, N-namylphthalimide, ethyl N,N-di-n-butylcarbamate, diethyl lauramide, dibutyl lauramide, lauroyl piperidine, N-nbutyl acetanilide, tetraethyl phthalamide, N-n-amyl sucketone, ,B-ethoxy ethyl acetate, ,8ebutoxy-p-ethoxy ethyl acetate, tetrahydrofurfuryl adipate, diethylene glycol monoacetate, fl-methoxymethyl acetate, acetonyl acetone, cyclohexanone, triethyl phosphate, diacetone alcohol, diethylene glycol monomethyl ether, ethylene glycol, di-

propylene glycol, acetone, ethanol, acetonitrile, dimethylformamide, dioxane, etc.

The hydrophilic organic colloid used in preparing the present emulsions or dispersions of dye developers as protective colloids include gelatin and its water-soluble derivatives, polyvinyl alcohol and its water-soluble derivatives and copolymers, water-soluble copolymers such as polyacrylamide, imidized polyacrylamide, etc., and other water-soluble film-forming materials that form water-permeable coatings such as colloidal albumin,

water-soluble cellulose derivatives such as ethanolamine Compatible mixtures of two or more such colloids can be utilized. Gelatin is preferred.

In preparing the photographic coating compositions of the invention comprising hydrophilic organic colloids containing dispersed droplets are high-boiling solventcontaining dye developers that have been treated with water-soluble sulfites, the dye developers are dissolved in solvents of the type described above and mixed with aqueous solutions of hydrophilic colloids. If desired, the water-soluble sulfite can be incorporated into the composition, or used in an aqueous wash to treat the composition, at this point. While the amount of solvent utilized to dissolve the dye developer can be widely varied, proportions of dye developer to high-boiling solvent in the range of about 1/ .25 to /2 on a weight basis The resulting oil-in-water emulsion is then emulsified or homogenized until the solvent containing the dye developer is substantially uniformly dispersed in finely-divided droplets, the droplets suitably being less than about 5 microns in a size, more generally less than about 2 microns in size and often times in the range of .5 to less than 5 microns in size.

The Water-soluble sulfite can also be added if desired during this emulsifying or homogenizing step. Small amounts of surfactant compounds can be utilized as dis dium diisopropylnaphthalene sulfonate, a sodium lauryl-I sulfonate, p-tert.-actylphenoxy diethoxy sulfonate sodium salt, p-tert.-octylphenoxydiethoxyethylsulfate tammonium salt, sodium N-methyl-N-oleyl taurate, diisobutylcresoxyethoxyethyl, dimethyl, benzylammonium chloride, diisobutylphenoxyethoxyethyl, dimethyl, benzylammonium chloride and the like. The resulting composition can be treated or washed with a water solution of a water-soluble sulfite at this stage of the preparation of the coating composition. The resulting dispersion can be chill-set, noodled and thereafter washed with water in accordance with usual photographic practice. Such compositions can thereafter'be treated or washed with a solution of a water-soluble sulfiite, or the watersoluble sulfite added directly thereto. A typical method for treating the emulsion composition at this stage is to melt the composition, add an aqueous solution of a water-soluble sulfite and maintain this mixture for a few minutes before removing the aqueous portion thereof.

Dye developer compositions thus prepared with the use of a water-solublesulfite treatment during its preparation as described above have substantially improved storage stability against dye developer crystallization and agglomeration as compared to dye developer dispersions prepared in the same manner without the use of the.

water-soluble sulfite. treatments.

The drawing illustrates a typical light-sensitive element or color film utilizing the dye developer dispersions of the invention. The drawing also illustrates a typical re:

ceiving sheet for receiving dye images from the light-senlayer 22 can be used to receive dye images from the lightsensitive element during processing when pressed in contact therewith. Positioned between the light-sensitive element and the receiving sheet is rupturable pod 21 containing processing material 20 such as a viscous alkaline aqueous composition. After exposure of the light-sen sitive element in -a camera to an image, rupturable pod 21 can be ruptured by passing the assembly illustrated in the drawing between rollers in the camera or remote from the camera and the processing composition in the pod uniformly distributed across a predetermined area of the light-sensitive element. The receiving sheet is pressed in contact with the light-sensitive element. The processing composition penetrates through layers 11 to 18, latent images develop in light- sensitive layers 12, 15 and 18 and dye developers in contiguous layers 11, 14 and 17 respectively rendered nondiffusing in areas corresponding to the latent image or negative areas, and' the dye developers in the remaining or positive image areas dilfuse imagewise in register to mordant layer 22, of the receiving sheet.

Light-sensitive elements of the type illustrated by the.

in the art and include such compounds as phenylhydro quinone, 2-hydroxyphenylhydroquinone, phenoxyhydroquinone, 4-methylphenylhydroquinone, dodecylhydroquinone, and the like.

Over layer.

Over layer 14 1 Over layer 15 is coated interlayer Over layer 17 is coated layer 18 com-' prising a blue-sensitive silver halide emulsion layer. Over layer 18 is coated protective layer 19. A receiving sheet comprising support 23 having coated thereover mordant Such light-sensitive elements are advantageously proce'ssed in the presence of onium compounds, preferably being contained in the alkaline processing composition or in the image reception element. Such onium compounds are also described in the artand include quarternary phosphonium, tertiary sulfonium and quaternary ammonium compounds.

The following examples will serve to illustrate my invention.

Example I.-Additin of water-soluble sulfite after washing dye developer dispersion A 12 g. portion of the magenta dye developer, 4-propoxy 2 [p-(fl-hydroquinonylethyl)-phenylazo] -1-naphthol, was dissolved in 24 cc. of cyclohexanone and 12 cc. of N,n-'butyl acentanilide by heating at 70 C. for about 20 minutes. To the resulting solution was added, with agitation, 120 g. of 10% aqueous gelatin and 12 cc. of a aqueous solution of the Surfactant, sodium diisopropylnaphthalene sulfonate. The resulting emulsion was passed through a colloid mill five times to uniformly disperse the suspended droplets of solvent containing the dye developer, substantially all the droplets being less than 2 microns in size. Suflicient water was added to bring the total weight of the resulting dispersion to 200 g. The dispersion was chill-set at 5 C., noodled, and washed for six hours with cold water. The drained noodles were then divided into two equal samples.

Example IA.To one-half of the above dispersion was added water (200 cc.), and this mixture was held at 40 C.

Example IB.One-half of the above dispersion was melted at 40 C. and 1% sodium sulfite (500.) was added; this solution was held for 15 minutes at 40 C., and then diluted with water (200 cc.), and the resulting mixture was held at 40 C. The dispersion stabilities of the samples of Examples IA andv IB are described in Table I of Example II below.

Example II.-Addition of water-soluble sulfite during preparation of dye developer dispersion A 9 g. portion of the magenta dye developer, 4-propoxy 2 [p-(fl-hydroquinonylethyl) -phenylazo]-1-naphthol, was dissolved in 18 cc. of cyclohexanone and 9 cc. of N,n-butyl acetanilide by heating at 70 C. for about 20 minutes. To the resulting solution was added, with agitation, 90 g. of 1% aqueous gelatin, 9 cc. of a 5% aqueous solution of sodium diisopropylnaphthalene sulfonate and 9 g. of anhydrous sodium sufite. The resulting emulsion was passed through a colloid mill 5 times at 70 C. to uniformly disperse the suspended droplets of solvent containing the dye developer, substantially all the droplets being less than 2 microns in size. Suflicient water was added to bring the total weight of the resulting dispersion to 200 g. The prepared dispersion was chill-set at 5 C., noodled, and washed for six hours with cold Water. The drained noodles were diluted with Water (200 cc.) and held at 40 C. The improvement in stability of the dye developer dispersions prepared according to Examples I and II can be seen from the following table. When judging -a sample for stability, the sample was considered to be stable until a substantial amount of particle agglomeration of dye developer had taken place.

TABLE I Stability 8 days--. 2 hrs. 7 wks--- 5% hrs. 5 wks-- 10 hrs.

1 0 As can be observed from the data set out in Table I, watersoluble sulfites are effective to stabilize dye-developer dispersions both when added to the dispersion during its preparation or when added following washing of the dispersion.

Example IlI.Addition of water-soluble sulfite during preparation of dye developer dispersion A 3 g. portion of the magenta dye developer, 4-propoxy-Z-[p-(B hydroquinonylethyl) phenylazo]-l-naphthol, was dissolved in 3 cc. of triethyl phosphate and 3 cc. of N,N-diethyllauramide by heating at C. for about 20 minutes. To the resulting solution was added, with agitation, 30 g. of 10% aqueous gelatin and 3 cc. of a 5% aqueous solution of sodium diisopropylnaphthalene sulfonate. The resulting emulsion was passed through a col- 'loid mill five times at 70 C. to uniformly disperse the suspended droplets of solvent containing the dye developer, substantially all of the droplets being less than 2 microns in size. This prepared dispersion is herein .referred to as Dispersion IIIA. A second dispersion, herein referred to as Dispersion IIIB, was prepared by the general method used to prepare dispersion IIIA except that 1 cc. of a 10% aqueous solution of sodium sulfite was added to the dispersion prior to passing through the colloid mill. Dispersions IIIA and IIIB were chill-set, noodled, and washed for six hours with cold water. The washed noodles were then diluted with water (200 cc.) and 5% sodium diisopropylnaphthalene sulfonate (0.2 cc.) were added. At 40 C., dispersion HIA formed crystals in 3 /2 hours and dispersion IIIB displaced crystals only after 6 /2 hours.

Example IV.A ddition of water-soluble sulfite during preparation of dy developer dispersions and after washing the dispersions A 30 g. portion of the magneta dye developer, 4-propoxy-2- [p- B-hydroxyquinonylethyl) phenylazo] -1-naphthol, was dissolved in 30 cc. of triethyl phosphate and 30 cc. of N,N-diethyllauramide by heating at 70 C. for about 20 minutes. To the resulting solution was added, with agitation, 300 g. of 10% aqueous gelatin, 30 cc. of a 5% aqueous solution of sodium diisopropylnaphthalene sulfonate and 10 cc. of a 10% aqueous solution of sodium sulfite. The resulting emulsion was passed through a colloid mill five times at 70 C. to uniformly disperse the suspended droplets of solvent containing the dye developer, substantially all of the droplets being less than 2 microns in size. This dispersion was chill-set, noodled, and washed with cold water for six hours. The dispersion noodles were then remelted at 40 C., and sodium sulfite (1%, 12 cc.) was added with stirring, the stirring being continued ten minutes. To 239 g. of this dispersion were then added sodium diisopropylnaphthalene 'sulfonate (2 cc., 5%) and water (765 cc.). No crystals in the prepared dispersion were observed during 10 hours at 40 C. compared to 6 /2 hours for Example IIIB dispersion. Also, no viscosity increases were noted in Examples III and IV.

Example V.-Treatment of dye developer dispersion with water-soluble sulfite A g. portion of the cyan dye developer, 5,8-dihydroxy-1,4-bis[(fl-hydroquinonyl a methyl)ethylamino] anthraquinone, was dissolved in 95 cc. of triethyl phosphate and cc. of N-n-butyl acetanilide. To the resulting solution was added, with agitation, 1110 g. of 10% aqueous gelatin, and 111 cc. of a 5% aqueous solution of the surfactant, p-tert.-octylphenoxydiethoxy-ethylsulfate ammonium salt. The resulting emulsion was passed through a colloid mill five times at 70 C. to uniformly disperse the suspended droplets of solvent containing the dye developer, substantially all of the droplets being less than 2 microns in size. The dispersion was then chill-set, noodled and washed 6 hours in cold water.

. into two equal parts.

remelted at 50 C., 7 cc. of 1% aqueous sodiumsulfite t sion prepared as described in Example VA.

Example VA.-T a 104 g. portion of the above dispersion (equivalent to 6 g. of dye developer) was added sodium sulfite (1%, 8.5 cc.) at 40 C. and the resulting dispersion held at 40 C. for 15 minutes. To 52 g. of this solution was added water (50 cc.) and sodium diisopropylnaphthalene sulfonate 0.5 cc.). A 40 C. holding of this mixture gave agglomeration after 15 hours.

Example VB.To a 52 g. portion of the original dispersion (equivalent to 3 g. of dye developer) was added water (50 cc.) said sodium diisopropylnaphthalene sulfonate (5%, 0.5 cc.). A 40 C. holding of this mixture gave agglomeration after 8 hours, thus showing the disadvantage of omitting the sulfite from the dispersion.

Example VI .---Treatment of dye developer dispersion with water-soluble sulfite A 30 g. portion of the yellow dye developer, 1-[4-hydroquinonylethyl]-phenyl 3-ethyl-carboxamido-4(2",4, 6"-trimethylphenylazo)-5-pyrazolone, was dissolved in 60 cc. of N-n-butyl acetanilide and 30 cc. of cyclohexanone.

To the resulting solution was added, with agitation, 300 g. of 10% aqueous gelatin and 10.5 cc. of a 10% aqueous solution of the surfactant, p-tert.-octylphenoxydiethoxyethylsulfate ammonium salt. The resulting emulsion was passed through a colloid mill five times at 70 C. to uniformly disperse the suspended droplets of solvent containing the dye developer, substantially all of the droplets being less than 2 microns in size. The resulting dispersion was washed 2 hours with cold water, drained and divided One portion of the dispersion was added, the pH adjusted to 7.0 and thereafter chilled. Both the dispersion portion containing the water-soluble sulfite and the portion free of the water-soluble sulfite were stored at 40 C. and compared with respect to stability. The dispersion containing the water-soluble sulfite did'not have crystals until 5 hours while the dispersion not containing the water-soluble sulfite displayed crystals after 1 /2 hours.

The above examples described the use of auxiliary water-soluble solvents such as cyclohexanone and triethyl phosphate, as well as water-soluble sulfite in making the dispersions and that during washing of the dispersions a substantial amount of the auxiliary solvent and watersoluble sulfite are removed. However, it is not necessary to wash the dispersions which have been treated with water-soluble sulfite since the stabilizing efiFect is not dependent upon the sulfite being removed by washing as demonstrated by Example VI above. Thus, dye developer dispersions can be prepared as described in Examples I to obtain the particularly useful low solvent ratio dispersions.

Example VII below illustrates the utility of the dye developer dispersions of the invention in a multilayer photographic element.

Example VII.A-multilayer photographic element containing dye developer dispersions of the invention A photographic color film having the structure substantially as shown in the drawing was prepared by coating a subbed cellulose acetate film support successively with the following layers:

(1) Cyan dye developer layer (e.g., layer No. 11 of drawing).A coating of the cyan dye developer disper- I gelatin layer,

(4) Magenta dye developer layer (e.g., layer No. 14 of the drawing).-A coating of the magenta dye developer dispersion prepared as described in Example IB.

(6) lnzerlayer (e.g., layer No. 16 of drawing).-A

gelatin layer.

(7) Yellow dye developer layer (e.g., layer No. 17 of drawing).A coating of the yellow dye developer dispersion prepared with the water-soluble sulfite as described -in Example VI.

(8) Blue-sensitive emulsion layer (e.g., layer No.18 of drawing).A coating of a developing-out negative gelatino-silver bromoiodide emulsion that is inherently sensitive to blue light.

(9) Protective layer (e.g., layer No. 19 of drawing). A gelatin coating containing 4'-methyl-phenylhydroquinone.

The described color film is exposed to a subject, and then processed by wetting with an aqueous solution containing 3.5% of high viscosity hydroxyethyl cellulose, 4% sodium hydroxide, 2% benzotriazole and 2% lphenethyl-Z-picolinium bromide with a dye image receiving sheet in contact therewith. After 2 minutes at 72 F., the color film and the receiving sheet. are stripped apart. A positive color image of dye developers is transferred to the receiving sheet. A suitable receiving sheet comprises a paper support carrying a gelatin layer containing a mixture of poly-4-vinyl pyridine mordant and I 1-phenyl-5-mercaptotetrazole.

Example VIII.Comparison of ascorbic acid and watersolable sulfite as treating agents for dye developer dispersions An 18 g. portion of the dye developer, 4-propoxy- 2-[p-(fl-hydroxyquinonylethyl)-phenylazo]-1 naphthol,

was dissolved in 36 cc. of cy-clohexanone and 18 cc. of:

N-n-butylacetanilide by heating :at 70 C. for 15 minutes. To the resulting solution was added, with agitatidn,

cc. of 10% aqueous gelatin and 18 cc. of a 5% aqueous 1 solution of sodium diisopropylnaphthalene sulfonate. The resutling emulsion was passed through'a colloid mill five times at 70 C. to uniformly disperse the suspended droplets of solvent containing the dye developer, substantially all of the droplets being less than 2 microns in size. The prepared dispersion was then chill-set at 5 C., noodled and washed for 6 hours in cold water. The

washed noodles were drained, remelted at 50 C. and

then divided into three equal portions (104 g. each) which were treated as described in Examples VIIIA-C below.

Example VIIIA (control sample).-An 87 g.portion of the original dispersion was diluted with 200 cc..of

water and the melt held at 40 C.

Example VIIIB.A 1% aqueous solution of sodium sulfite (5 cc.) was added to the original dispersion and the resulting mixture stirred for 10 minutes. A 91 g. portion of the resulting dispersion was diluted with 200 cc. of water and the melt held at 40 C.

Example VIIIC.A 1% aqueous solution of ascorbic acid (7 cc.) was added to the original dispersion and the resulting dispersion held for 10 minutes. A 97 g. portion of the resulting dispersion was diluted with 200 cc.. of water and the melt held at 40 C.

The dispersion of Example VIIIB exhibited agglomeration by microscopic examination only after 4.5 hours, while Example VIIIC exhibited agglomeration to unmagnified visual observation in 1 hour.

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

I claim:

1. The process for preparing photographic compositions which comprises dissolving in a water-immiscible organic solvent boiling above about 175 C. a photographic dye developer having in the same molecule both the chromophoric system of a dye and a hydroquinonyl moiety capable of developing photographic silver halide, and substantially uniformly dispersing the resulting solution in finely-divided droplets in an organic hydrophilic colloid, said dye developer having been treated with a water-soluble sulfite during said process.

2. The process as defined by claim 1 wherein the wator-soluble sulfite treatment is effected with about .001 to .65 mole of water-soluble sulfite for each mole of dye developer treated.

3. The process for preparing photographic compositions which comprises dissolving in a water-immiscible organic solvent boiling above about 175 C. a photographic dye developer having in the same molecule both the chromophoric system of a dye and a hydroquinonyl moiety capable of developing photographic silver halide, and substantially uniformly dispersing the resulting solution in finely-divided droplets less than about microns in size in aqueous gelation, said dye developer having been treated with about .001 to .65 mole of a watersoluble sulfite for each mole of said dye developer during said process.

4. The process as defined by claim 3 whrein watersoluble sulfite treatment is effected by adding water-soluble sulfite to the organic solvent solution of dye developer and gelatin prior to dispersing the mixture.

5. The process as defined by claim 3 wherein watersoluble sulfite treatment is effected by adding water-solable sulfite to the dispersion of droplets of organic solvent solution of dye developer in the gelatin.

6. The process as defined by claim 3 wherein watersoluble sulfite treatment is effected by adding water-sebuble sulfiite to the dispersion of droplets of organic solvent solution of dye developer in the 'geletin whilea htn solvent solution of dye developer in the gelatin while the dispersion is in molten form.

7. The process as defined by claim 3 wherein an auxiliary solvent is utilized with the water-immiscible organic solvent to dissolve the dye developer, said auxiliary solvent being selected from the group consisting of (1) a water-soluble organic solvent, and

(2) a substantially water-insoluble organic solvent having a boiling point at least about 25 C. below the boiling point of the water-immissible organic solvent.

8. The process as defined by claim 3 wherein the water-soluble sulfite is sodium sulfite.

9. The process as defined by claim 3 wherein the organic solvent is selected from the group consisting of (1) N-n-butyl acetanilide and (2) ,N,N-diethyllauramide and the dye developer is selected from the group consisting of (l 4-propoxy-2-( ,B-hydroquinonylethyl) -phenylazol-lnaphthol,

(2) 5,8-dihydroxy-1,4-bis[ ([3 hydroquinonyl-a-methyl)ethylamino] anthraquinone and (3) 1-[4'-hydroquinony-lethyl] phenyl 3 ethylcarbamido 4 (2",4",6"-trimethylphenylazo)-5-pyrazolone.

10. A photographic composition comprising an organic hydrophilic colloid containing substantially uniformly dispersed therein finely-divided droplets of a water-immiscible organic solvent boiling above about C., and dissolved in said solvent a photographic dye developer having in the same molecule both the chromophoric system of a dye and a hydroquinonyl moiety capable of developing photographic silver halide, said dye developer having been treated with a water-soluble sulfite.

11. The product as defined in claim 10 wherein the dye developer has been treated with about .001 to .65

mole of a water-soluble sulfite vfor each mole of said dye developer in said composition.

12. A photographic composition comprising aqueous gelatin containing substantially uniformly dispersed therein finely-divided droplets less than about 5 microns in size of a water-immiscible organic solvent boiling above about 175 C., and dissolved in said solvent a photographic dye developer having in the same molecule both the chromophoric system of a dye and a hydroquin-onyl moiety capable of developing photographic silver halide, said dye developer having been treated with about .001 to .65 mole of a water-soluble sulfite dor each mole of said dye developer in said composition.

13. A photographic composition as defined by claim 12 wherein the water-soluble sulfite is sodium sulfite.

14. A photographic composition as defined by claim 12 .wherein the organic solvent is selected from the group consisting of (1 N-n-butyl acetanilide and (2) N,N-diethyllauramide, and the dye developer is selected from the group consisting of (1) 4 propoxy-2-[p-(B-hydroquinonylethyl) phenylazoJ-l-napthol,

(2) 5,8-dihydroxy-1,4-bis[l(,d-hydroquinonyl-a-methyl) ethylarnino] anthraquinone and (3) 1-[4'-l1ydroquinonylethyl] phenyl 3 ethylcarbamido 4 (2",4",6" trimethylphenylazo 5- pyrazolone.

15. A photographic element comprising a support having coated thereon at least one silver halide emulsion layer having contiguous thereto a layer of the photographic composition defined by claim 10.

16. A photographic composition comprising an organic hydrophilic colloid containing substantially uniformly dispersed therein finely-divided droplets of a water-immiscible organic solvent boiling above about 175 C., a photographic dye developer having in the same molecule both the chromophoric system of a dye and a hydroquinonyl moiety capable of developing photographic silver halide being dissolved in said solvent, and a watersoluble sulfite.

References Cited by the Examiner UNITED STATES PATENTS 2,360,290 10/ 1944 Vittum et al 9656 2,983,606 5/1961 Rogers 96100 FOREIGN PATENTS 221,880 8/1957 Australia. 606,417 10/ 1960 Canada. 804,971 11/ 1958 Great Britain.

NORMAN G. TORCHIN, Primary Examiner. J. T. BROWN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,287,133 November 22, 1966 Carl J. Williams, Jr.

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 13, line 42, for "gelation" read gelatin line 46, for "whrein" read wherein line 56, for "sulfiite" read sulfite line 57 strike out "solvent solution of dye developer in the geletin whilea*htn"; line 68, for "immissible" read immiscible column 14, line 3, for "(B-hydroquinonylethyl) phenylazol" read [p-(B- hydroquinonylethyl) phenylazo] line 48, after"'trimethylphenylazo" insert a closing parenthesis.

Signed and sealed this 12th day of September 1967.

(SEAL) Attest:

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

Claims (2)

10. A PHOTOGRAPHIC COMPOSITION COMPRISING AN ORGANIC HYDROPHILIC COLLOID CONTAINING SUBSTANTIALLY UNIFORMLY DISPERSED THEREIN FINELY-DIVIDED DROPLETS OF A WATER-IMMISCIBLE ORGANIC SOLVENT BOILING ABOVE ABOUT 175*C., AND DISSOLVED IN SAID SOLVENT A PHOTOGRAPHIC DYE DEVELOPER HAVING IN THE SAME MOLECULE BOTH THE CHROMOPHORIC SYSTEM OF A DYE AND A HYDROQUINONYL MOIETY CAPABLE OF DEVELOPING PHOTOGRAPHIC SILVER HALIDE, SAID DYE DEVELOPER HAVING BEEN TREATED WITH A WATER-SOLUBLE SULFITE.

15. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING COATED THEREON AT LEAST ONE SILVER HALIDE EMULSION LAYER HAVING CONTIGUOUS THERETO A LAYER OF THE PHOTOGRAPHIC COMPOSITION DEFINED BY CLAIM 10.

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