US2940849A - Planographic dye transfer process - Google Patents

Description

June 14, 1960 K. E. WHlTMORE ETAL 4 ,84

PLANOGRAPHIC DYE TRANSFER PROCESS Filed July 10, 1957 SILVER HAL/0E IMAGE Sfage OOLO/fi DEVELOPMENT (/O/V/C COUPL ER) KE/TH E WH/TMO/PE JOH/V W/LL/AMS INVENTORS ATTORNEY 8 AGE/VT mted States PLANOGRAPHIC DYE TRANSFER PROCESS Filed July 10, 1957, Ser. No. 670,896

18 Claims. (Cl. 963) This invention relates to a photographic process for reproducing subjects which involves the preparation of ionic dye images in photographic emulsion layers, the dyeing of the images with ionic dyes and printing from the dyed images by imbibition dye-printing methods.

The imbibition dye-printing process of color photography is well known. In a common form of the process, colloid matrices such as gelatin relief images are prepared from color-separation images and after dyeing the matrices with dyes of appropriate colors, the dyes are transferred imagewise by imbibition from the matrices to a mordanted receiving surface in register. Dye transfer processes of this type depend on the formation of a relief image in gelatin by a variety of means which have one point in common, the exposure of an emulsion containing such a high concentration of dye or pigment that the exposure varies rapidly with the distance to which light has penetrated the emulsion. By means such as a tanning developer, a tanning bleach bath, or an etch bath regulated by concentration of silver, the gelatin of the emulsion at points containing a critical concentration of silver is either tanned or made soluble, so that on development with hot water a relief image is formed in varying thicknesses of gelatin. This is used to absorb dye which is transferred to a receiving sheet. These relief processes have been and are used on a large scale commercially, but they have several difiiculties. In the first place, the high light-absorption of the emulsion greatly decreases its sensitivity, and, combined with the hot Water development, gives a very unfavorable relation of speed to definition. The images are physically soft, and all types of these processes are diificult to control, especially with the precision necessary for three-color photography. When used for cine film or other small images, the relief image may give difiiculty of contact with the blank.

We have discovered a process of transferring dye images by imbibition from planar colloid surfaces as opposed to the colloid relief image surfaces. The process employs ordinary sliver halide emulsion which need not contain a dye or pigment to lessen speed. Other disadvantages mentioned above associated with the exposure, tanning development and bleaching operations of the colloid matrix processes are avoided in the process of the invention.

According to our invention an imagewise distribution of developable silver halide is prepared in an organic colloid layer, for example, by means of light exposure of an ordinary silver halide emulsion layer. The silver halide image is then developed with a color developing solution containing aprimary aromatic amino. silver halide developing agent, in the presence of an ionic coupler compound; such, as a sulfonated pyrazolone coupler below, reactive with the oxidation product of the developing agent to fonn ionic dye image in the layer which is substantially non-diffusing or has a low rate of diffusion in the colloid layer particularly with. regard to the dye subsequently used in the process. The ionic character may be imparted to the dye either by use of an ionic coupler or ionic developing agent, or by both. The color of the ionic dye image'is not important. Thereafter, the ionic dye image is dyed up with a difiusible ionic dye of charge opposite to that of the dye image, for example, a basic dye if the image is anionic thereby forming a salt of the ionic dye and the dye of opposite charge. Thereafter the colloid layer containing the dye image is placed in contact with a receiving element containing a mordant for the ionic dye and a transfer of the ionic dye is made to the receiving element by imbibition methods. Repeated transfers can be made similarly by merely recharging the ionic dye image with the ionic dye. Accordingly, the process employs an ionic dye image in place of the usual colloid matrix for obtaining an imagewise distribution of transferable dye.

The invention is illustrated in the accompanying draw-' ings wherein in Stage 1 is shown in greatly enlarged cross-sectional viewthe appearance of a typical photographic element comprising a support 10 such as a cellulose acetate film support, carrying the hydrophilic organic colloid layer containing a developable silver halide image 12 such as contained in an exposed silver halide emulsion layer. The silver halide image is developed with a colorforming developer composition in the presence of the ionic-coupler compound. (anionic or cationic) to obtain the element shown in Stage 2' containing the dye image 13 in layer 11. Thereafter the element of Stage 2 is treated with a solution of an ionic dye of charge opposite to that of the dye image 13 producing the composite dye image 14 as shown in Stage 3. Subsequently, layer 11 of the dyed element while moist is placed into contact with the imbibition blank shown in Stage 4 having a support 20 and organic colloid layer 21 containing a mordant for the ionic dye, with the result that the imbibition dye image 15 is obtained in the imbibition blank.

In the process of the invention, various photographic elements containing the imagewise distribution of developable silver halide may be used. The element may take the form of a sensitive film which has been exposed and a silver image developed therein leaving the usual undeveloped silver halide image in the emulsion for use in the process. This procedure is particularly useful to replace the well-known imbibition dye-printing process employed for the production of colored motion-picture films. In that process, gelatin relief matrices corresponding to primary color-separation images are prepared for example from color-separation negatives. The matrices are then dyed with subtractively coloreddyes and the respective dye images printed successively by imbibition in register on an imbibition blank. According to the present invention, in a similar process the gelatin matrices may be replaced by an equal numberof silver halide emlusions in which have been recorded the color-separation images followed by color development of ionic dye images in each, dyeing each of the resulting ionic dye images subtractively with an. ionic dye of charge opposite that of the dye images and then printing each dye image onto a mordanted imbibition blank in register. This color reproduction process may be carried out by making original color-sepaa'tion negatives directly from a scene being photographed and printing positive films therefrom whichare separately, color-developed to produce the ionic dye images for use as described; otherwise the color-separation colored image 'in natural color.

' fi oin any silver image 'on an imbibition blank images to be color-developed to ionic dye images may be derived by the filtered exposure of sensitive films to color transparencies such as the Eastman Color Negative describedvby Hanson and Kisner, I.S.M.P.T.E. .61, 667401 (1953). Color negatives of that type contain color-separation images recorded in a multilayer color film in the form of subtractively colored negative dye images. Such color negatives can therefore be used to print'color-separation positiveimages into separateisensi tive films which, according to the present invention, are then' color-developedto produce the ionic dye images'in each which arethen dyed with s'ubtractivcly colored dyes of' opposite charge and thereafter each dye image is printed by imbibition methods onto 'a mordanted imbibition blank in register to obtain a positive subtractively This procedure is'dcscribed in more detail in Example 1 hereinafter.

Similarly, the reproduction may be made from a positive image by using'reversal methodsiorbytheuse of direct positive emulsions. Thus a' positive imagemay be used toexpose an emulsion which is then developed with. a

black-and white developer followed by reversal exposure and color development .to produce the ionic dye image which is utilized'to make a dye transfer print as described. When the positive consists of a positivecolor transparency such as is produced by well-known methods in multilayer i substractive color films; and a subtractively colored print be'obtained by the process of is'jdesired,''the same may the invention by recording color separa tion negative images in separateifilms by filtered exposureiof the transparency, developing each film toisilve'r images, reversal exposing, color developing the same or a different ionic dye image in; each of the films using a suitable ionic con pler, followed by dyeing the ionic dye images subtractively and transferring the dyes to an imbibition blank in register.

The process may be carried 'out similarly by starting v such'as a silver color-separation image andmerely bleaching the silver image by wellknown methods to produce-an imagewise distribution of developable'silver halide in the film which is then colord'evel oped to, produce the ionic dyeimage which is then used'as a planographic element for printing a dye image as described. Thus, well-known motion-picture color-separation colloid relief matrices containing silver images,';formerly 'used for the printing of subtractively colored dye images by the inhibition dyeprinting process, may be bleached'topro'duce silver halide images distributed in the films in proportion to the silver and colloid relief images therein and the silver halide images developed to ionic dye images which are then dyed subtractively with ionic dyes and printed by imbibition.

v .This process is therefore notdependnt upon the absorption of the image dye by the colloid relief'ima ge and the transfer of the dye therefrom is not dependent upon the relief image itself. Rather, the image dye may be controlled by the ionic dye image alone independent of the colloid relief image; although unusual effects are obtainable by use of a mixture of dyes for coloring the relief images containing the ionic dye image such as one dye which is controlled by the ionic dye image itself and another dye controlled by the colloidrelief image. Accordingly a much wide'r'choice of dyes can be employed and the undesirable eflects upondefinition of imbibition prints associated with dye transfer from relief images are obviated by the present planographic dye transfer process. 7 a I V V The process of'th'e invention can be carried out in a somewhat difierent manner byemployingas the sensitive element in which the imagewise distribution' 'of developable silverhalide is formed, an emulsion containing ja substantially non-diffusing anionic coupler compound'having an acid group in a non-coupling positionand whichcoupler is reactive with a color-forming developing agent presen! in t pe o t n to produce dy in a eadi ily soluble in the alkaline processingsolutions."Suclra'coua pler is 1-pheny1-3-(3-su1fobenzamido)-4-(4 octadecyloir'yphenylazo) S-pyr'iazolone, having the formula:

NHCO-O The result is that during color development of the emulsion containing the coupler and subsequent processing steps; the dye image'obtained in the developed area Washes ,out of the emulsion leaving an imagewise distribu-r tion of the original anionic coupler in the emulsion which may be dyed with a-basic dye for transfer byimbibition to a mordanted receiving sheet as shown in Example 6 hereafter.

V CHzCHiSOaH coon i n p 1- (3-car'p oxy-et-hydroxyphenyl) 3 -phenyl-5 -p'yrazolone -c o oHgoN V l-hydroxy N- [)8- (3 -sulfobenzarnido) ethyl] -2-'naphthamide l-hydroxvN-(B-sulfoethyl)-2=naphthamide l hydroxy -N ('4-hydroxy 3carboxyphettyl) -2-naphthal-( 3 -pho'sphonophenyl) -3 -undecyl-5 '-pyrazolone l-hydroXy-N,-( 2,3 -dicarboxyphenyl) -2-naphthamide l-hydroxy-N- [4-'( fi-sulfo ethoxy) phenyl] -2-naphtharnide l hydroxy-naphthoic acid 5-methoxy-2-(3-sulfobenzamido).phenol l-hydroxy- N (m=hydroxyphosphonophenyl)-2-naphthamide l-hydroxy N {o-[';8-(,8-sulfoethoxy)e naphthamide '1 -hydro'x'y 3'[ (B-sulfoethyl)sulfamyllphenyl briaphthamide l-hydrox'y-N-[1B43,5 disulfobenzamidolethyll 2naphtha- -'mide 1' meuirem th iphes ne nadeeyi-yp razeieae oon'nomonzonfmcnm 6.50011,

l-h ydroxy-N- [3- (N ,N,N -trimethylam1nopropyl) J-Z-naphthamide-p-toluene sulfonate Accordingly, it will be understood that the ionic couplers, in addition to possessing ability to couple with color developing agents, contain in the case of the anionic couplers, a negative charge for example due to the presence in the molecule of an acid group such as SO H, P(OH) As(OH) COOH etc., attached either directly to the nucleus or to a side chain in a non-coupling position, or in the case of the cationic couplers possessing a positive charge due to the presence of the coupler molecule of a basic group such as an ammonium group in a non-coupling position of the molecule. i

The well-known primary aromatic amino silver halide developing agents of the para-phenylenediamine type are useful in developing the ionic dye images with the ionic coupler compounds, for example, Z-amino-S-diethylamino toluene as well as nmQir-ommnsomn- C H; -amino-N-ethyl-3-methyl-N-(fi-sulfonamidoethyl) aniline CzHs HaNOId-4CH2MCOOH CH: 4-amino-N- 10-carb oxydecyl) -N-ethyl-3-methyl aniline Other very useful developing agents are as follows:

In case the coupler compound used is non-ionic or not strongly anionic such as on c n o omUNnoom 1,3-di (l'-hydroxy-2'-naphthamido) benzene the color developing agent should be an ionic one such as 4-amino-N-( IO-carboxydecyl)-N-ethyl-3-methyl aniline above as shown in Example 2 below.

Representative basic dyes suitable for anionic dye images include the following Acridine Yellow (Color Index 785) Auramine G (Color Index 656) Auramine (Color Index65 5) CapribIau GON (Color Index 876). Chrysoidine Y (Color Index Methylene Blue GX' (Color Index 922) s' New Fast Green 2B (Color Index 659) Rhoduline. Blue 6GA (Color Index 658) dyeing up the 3 Thiofiavine T (Color Index 815) Malachite Green (Color Index 657) Acriflavine (Color Index 790) Astraphloxine FF (Schultz-Lehmann 930) Brilliant Alizarine Light Red 4B, is a typical magenta acid dye useful for dyeing up the cationic dye images produced in the process of the invention imbibition trans- .fer as described. Other acid dyes are readily selected to provide subtractively colored cyan and yellow acid dye images. 7

The mordants useful in the imbibition blanks to which the basic dye images are transferred include those known in the art for example silicotungstic acid, phosphomolybdic acid, phosphotungstic acid, a styrene-maleic anhydride copolymer (1 to 1), polyvinyl phthalate, sulfonated polystyrene, or other high molecular weight anionic material which combines with the cation of the basic dye. Particularly effective mordants may be selected from the sulfonated and carboxylated compounds disclosed in the Saunders et al. US. Patent 2,756,149 having the general formula NHCOR:

GOQNHCOQ I 0 soul Q 5- [4-(2,4-di-tert-amylphenoxy)-3- (phenylcarbamyl) phenylcarbamyl]-l,3-benzenedisu1fonyl chloride 0511 1-15 SOsH t-HHOQ-O NBC 06 on I :0 503E CCNHCHzCHr-ONH 1 hydroxy-4-chl0ro-N-{4-[2 -(2,4-di-tert. amyl henoxy)-5-(3,5 glisodiigm sulfobenzamido) benzamido] ph enethyU-2-napham e CH C

application Serial No. 544,111 filed December 19, 1955,

now 2,882,156, having the structure CHFCH l= N---N'HC-NH| dn, ucmooon 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 October 11, 13949.' 7 a;

. 3-methyl aniline and bromide bleach solution A finer-grain positive film was, exposedto a negative scenesa red-light color-separation image from *a multzi- "layer ccfilorjegative, followed by development at 80': 1F or Q minutes-in a wave tionalalkalinecarbonate I 'loping so'1ution containing 5.4 grams perditer of the developing agent 4-amino-N-(l0-carboxydecyl) N-ethyl- 2.75 grams per liter of the anionic coupler 1 hydroxy -'N EZ-(B-sulfoethoxylrihenyl] -2- naphthamideto formthe anionic dye imagein theeic posed'area, followedby rinsing the film for 30 seconds, fixing-it for-imimrtes in conventional hypo solution, wash- "ing for 3minutes, bleaching for 1 minute in a ferricyanideof composition given in Example and'refixing the stripifor 1 minute '6 rinsing for 30 seconds,

' beforthe final wash.

The resulting dye matrix, containing image ONE? oniongsoin V ll ' carts-(ammo 0 on was-bathed 2 "removed from placed in contact with a receivingfilm which had been the anionic dye minutes in 'asolution'ofMethylene Blue'dye,

' preconditioned with acetic acid solution before. use and having a gelatin coating containing an acid mordant, e.g., 1 hydroxy-4-ch-loro-N-{L ['2(2,4-di-tert;-amylpheuoxy)- 5 (3,"5 disodiurn sulfobenzarnido):benzamido] -phenethyl}-2-naphthamide (Sanders et al. U.S. Patent 2,- 756,149). The dye transferred from the anionic dye image to therreceivinggsurface'with gooddefinition. Additional prints Were'obtainedby'repeating thedyebathing, rinsing and transferring steps to obtain :a series of cyan colored prints of nearly identical density and contrast.

In a similar manner, greenand blue light color-separation images of thesame subject-were used for the prepartion of anionic dye images in separate sensitive films and dyed respectively with magenta and yellow basic dyes such as Sevron BrilliantgRed 4-K Genaciyl Yellow 3G or Sevron Yellow R. The magenta and yellow dyes .were then transferred to the mordanted receivingfilm in register with the cyan image from the red color-separation to obtain a full-co-lorreproduction ofthe subject. Asmentio-ned :in these examples, a variety of means the dye bath, aimed for '90 seconds and may be used for supplying the silver halide image'which is developed to the. ionic dye image. negatives orpositives and filtered negativeor positive color transparencies may be used .for exposure of the sensitive -elementsrin=which the ionic dye images are formed. When desired, reversal processing may be employed, for example, when preparing the ionic dye images by printing directly :frommositiveoriginals.

Example 2 A fine-grain positive film was exposed-to a negative I such as a red-light'color-separation image, developed 5 minutes at 9.0? F. in a 'conventional alkaline'carbonate developer solution containing 3.0 grams per liter of 4- zamin'o N- sisulfoethylrN-ethyl-methyl aniline and 3 *grams :per .liter :of LB-idi :(1 -'hydroxy.-2maphthamidn)tl henzenalfixing in amonventional hypo ghath, washing. 3 minutes. bleaching in an ordinary Color-separation iHr N-.UIEiSUSNa wasibathed in a solutionof Methylene-Blue dye,'ren1oved from the-dye bath, rinsed and placed in contact with-a receiving film (preconditioned to acetic acid) having va gelatin coating containing'an acid 'm'ordant, e.g., phos- 'photungstic acid. 'The dye bathing, rinsing, and transferring operation was repeated several times yielding aseries of'monochrom'e cyan printsgof very nearly identical density and contrast. 7

in "a .similar =manner, "green and blue-light colorseparation images of the-same subject were used for preparation'of anionic dye images in-separatesensitive films and dyed with magenta'andyellow dyes of Example 1 and transferredinzregistento the imbibition blank containing the cyan image to obtainaiull-color reproduction of the subject.

Example "3 The process of Example 1 "was carried out except using positive images for'exposure of thefilms, developing the films in. a conventional black-and-white developing solution for 10 minutes at 68 F, washing'S minutes, reversal exposing teach film followed by :the :same color developing, fixing, bleaching, washing, drying andtransfer steps of Example 1 to obtain registered. subtractively colored images corresponding to the original positive images. Example 4 y Thisexample illustrates a typicalprocedure:employing a cationic dye image and acid dyes. V

A fine-grain positivefilm was exposed to v:anegative such -as .a red-light color-separation image, developing for 1.0 minutes at,68 vF. infan alkalinecarbon'ate developer containing 3.4 grams per liter of 4-amino-N- (l0- carboxydecyl) -N-ethyl-3-methylaniline and 3.0 grams per liter vof l-hydroxy-N- [3-N,N,N-trimethylaminopropyll-2- naphthamide iodide, rinsing the strip for 30 seconds, 'fixing it for 3 minutes in hypo, washing for 3 minutes, bleaching for 30 seconds in the ferricyanide-bromide bleach, and refixing the strip for 1 minute before the final wash.

The resulting rye matrix containing a cationic dye image was then bathed ina solution of Brilliant Alizarin Light Red 48 magenta dye, removed from the' dye bath, rinsed and placed in contact with a receiving film having a gelatin coating. containing a polyvinylaminoguanidinc mordantmentioned above. The dyebathing, rinsing, and transferring operation was repeated several times yielding a series toimonochrome magenta prints of very nearly identical density .and contrast.

In a similar manner green and blue-light color-separation images of the same subject may be utilizedto obtain cationic dye images "for dyeing with magenta and yellow acid dyes for transfer iniregister' tcthe 'cyan' image on the receiving film.

Example 5 The procedure nfiaample 4 wasrcarriedinut except using thef nationic lEhydIOXy .QZqryridyD-Z- 9 naphthamide methyl p-toluene sulfonate in the color developing solution for each film in place of the quaternary ammonium coupler and replacing the color developing agent with a like amount of Z-amino-S-diethylaminotoluene.

The procedures of Examples 4 and 5 can be carried out similarly employing positive originals and using the reversal process, by inter-posing black-and-white development and reversal exposure steps before color development.

Example 6 The mentioned variation of the invention wherein the emulsion contains an anionic coupler containing an acid group in a non-coupling position of the molecule is illustrated in this example.

400 milligrams of the coupler l-phenyl-3-(3-sulfobenzamido) -4-(4-octadecyloxyphenylazo)- 5 pyrazolone was moistened with ethyl acetate and ethyl alcohol with the addition of concentrated ammonia to efiect solution. This solution was added to 20 cc. of 10 percent aqueous gelatin solution and to this was added a small amount of a spreading agent. The pH of the solution was then adjusted to 6.5 and 30 cc. of a silver bromoiodide emulsion added followed by stirring for 10 seconds, holding for minutes at 40 C. and coating on a cellulose acetate film base.

1 Samples of the resultant film were then exposed with white light to color-separation positive images which had been made from a multilayer positive color transparency. Each sample was then treated in the following process at 70 F. (unless otherwise indicated): Develop 10 min. Rinse 1 min. Fix l min. Wash 3 min. Bleach l min. Wash 10 min. Harden 4 min. Dry.

Wash 10 min. Bleach (15% HCl) 5-10 see. at F. Wash.

Dry.

The film now containing anionic positive dye images composed of the residual color coupler (the dye formed in color development having washed out of the emulsion) was then dyed for 5 minutes in 0.25 percent aqueous solutions of dyes complementary in color to each color a separation, that is, Methylene Blue, Safranine O and Acraflavine dyes, followed by rinsing 3-20 seconds in 0.5 percent acetic acid solution. Thereafter, in order to obtain a multicolor reproduction in full color the yellow, magenta and cyan dye images were transferred from the films for 5 minutes each in register on a mordanted imbibition blank prepared as follows:

300 milligrams of the mordant CHI CHa CisHss KSOPCHP] CH on "10 The processing solutions used in the above process had the following compositions: G.

Developer:

Calgon 1.0 Sodium sulfite 4.0 2-methyl 4 N',N diethylamino-aniline hydrochloride p 3.0 Sodium carbonate (mono.) 20.0 Potassium bromide 2.0 Sodium thiocyanate 2.0 Water to 1.0 liter.

Formalin hardener:

Calgon g 0.6 Sodium bisulfite g 5.0 Sodium carbonate g 5.0 Potassium bromide g 1.0 40% formaldehyde rnls 20.0 Water to 1.0 liter. Bleaching solution: G. Potassium ferricyanide 30 Sodium bromide 13 Borax 7.3 Boric acid 15 Sodium nitrate 30 Water 1 liter.

Fixing solution: G. Sodium thiosulfate (hypo) 240 Sodium sulfite (des.) 10

- Sodium bisulfite Water-l liter. 1

In the above processes the bleach (15 percent HCl)" is used to remove any residual color-developed dye which may not have washed out of the film previously.

It will be apparent that if the coupler-containing films are, to be exposed to color-separation negatives for the production of multicolor prints, the black-and-white development'and reversal exposure steps of the reversal technique can be employed in the process of this example prior to the color-development step.

The ionic dye images prepared as described above are useful in a similar color process. That is, in multilayer color films in which the blue-sensitive emulsion layer for the production of the yellow image is outermost, the emulsion causes scattering of light which exposesan underlying emulsion layer thereby causing a loss in definition. To remedy this efiect, the silver halide content of the blue-sensitive emulsion layer may be reduced appreciably to reduce the light scattering and a yellow ionic dye image of low density developed in the layer using an ionic yellow-forming coupler such as e-benzoyl-4-(3- chlorosulfonylbenzamido) acetanilide and developing with, for example, 2-amino-5-diethylaminotoluene monohydrochloride. The resulting yellow ionic dye image may then be dyed to the required density and contrast using a solution of a yellow dye of opposite charge such as those above mentioned.

What we claim is:

1. A photographic reproduction process which comprises developing a gelatino layer containing an image- Wise distribution of developable silver halide, with a silver halide developing solution containing a primary aromatic amino silver halide developing agent in the presence of a coupler compound reactive With the oxidation product of said developing agent to form an imagewise distribution of a substantially non-difiusing dye of the class consisting of acid and basic dyes in the layer, bleaching the resultant silver image and fixing, dyeing the dye image thus formed with a diifusible dye which forms a salt with said dye image, placing the colloid layer while moist into contact with a receiving layer containing a mordant for said last-mentioned dye and transferring the dye image-wise by imbibition to the receiving layer.

2. A photographic reproduction process which com- -in'g agent and a coupler compound poundireactive wise distribution of asubStantiaIly non-difiusing-dye of l the class '-consistin'g of acid and basic dyes "in the layer,

bleaching the resultant silver image andfixin'g; dyeing the dye image-thus formed --with wvhile-moist into contact with-a receiving layer containing a mordant for said 'last-rnentioned'dye-and transfer-' a 'diifusible dye which forms 7 a-=salt-with said dye image, placing the emulsion :layer 'ring the dye 'imagewise by imbibition .to the receiving .:layer.

3; jA photographic rcproductionfprocess ,which com- ;prises exposing a gelatino silver halideemulsion layer to :a colorseparation image of a colored subject, developing the-exposed emulsion layer with a silver halide developing solution containing a primary aromatic, amino silver. halide developing" agent and a coupler compound reactive with "the oxidation product of said developing agent to form an image-wise distribution of a substantially nomdiifusing dye of the class consisting of acid and basic dyes in the layer; bleaching the resultant silver image and fixing, dyeing the dyeimage thus formed witha difius abledye which 'forrns a -'saltwith said dye image,

V placing the emulsion layer while moist into contact with a receiving layercontainin'g a mordant for said last-mentioned ,dye and translfelimlg fl l mas by lb QH'tO theireceiving zdayer V A; photq ap release; r e ich prises exposing a plurality of gelatino silver ha'lideemulsionlayers ongseparate supports each to ditferentprimary color separation imagesof'a colored 'subjecg de velopingeach' of the exposedemuls ion layers with asilver halide developing solutioncontaining 'a primary aromatic 12 -119- Ihe m rass of .cla m ,1 wherein the gelafin laye containing-an imas wise .disrribiition f d velo esil fl halide jasi ref halide emulsion l yer 'wh c. j cxposedto -.a -.color. sep atioaitnage f pos t w colo transparency, developed; and the residual silver halide rcver ale nose 7 a 1l-1T11e1PIZ0CQSS-.Q i erein e couple bqm- 119 111 i .;l-,. editl'i ydroxyfl'rnaphthamid lbenz ne nd the eveloping'ra nt is 41amin -N-fl y m y -N-(Br snlfoethyDaniline. r s 12. The process of claim 2 wherein the coupler'compound is l-hydroxy-N- [2-( j3-Sl1lfO8thQXy) phenyl] -2-naphthamide and the developing agent is 4-amino-N-(l O-carbony'decyl) "-N-ethy1-3-methylaniline. l 3."I'he process -of claim 2 wherein the developing agent is strongly acidic and reacts withthecouplercompound to form a strongly acidic dye image which is dyed with-abasic dye.

aminosilver halide developingagent and a'coupler comwith theoxidation product of said never- Ioping-agent to form a' dye image of'a-substantiallynon- "sing fdyeofthe' class consisting of :acidand'basic dyesin 'each emulsion layeigbleacihing'the; resultant'silver image and fixing, dyeing each ofthe resultingdye images withja -difiusihle 'dye' which forms a saltiwith' said dye imageand which has a'color complementary, to the color 7 or light-used in formingeachicolorseparation image, and

. 'transferring the last-mentioned dyesfrom each layerby diffusion "to an 'imbibition blank in register, said imbibiltion blank "containing mordant's for :said last mentioned containing an irnagewise distribution of developable silver halide is a silver halide emulsion layer; which has been exposed, developed, and the residual silver halide reversal exposed. V

14.The process (if-claim '2 wherein the'coupler compound is one containing a phenolic hydroxy group.

ISiThe process of claim 2 wherein the coupler'compound isa 5-pyrazolone.

1'6."The-process ofclaim '2 wherein thecoupler compound; is 7 one containing an open-chainreactivemethylene v:group.

'17. A photographic; reproduction process which comprises exposing a gelatino silver halide emulsion layer containing a strongly acidic coupler compoundreactive with the oxi'dation product of flaPl'llIlBJfY aromatic amino silver halide-{developingagent to form an alkali-soluble dye irna-ge, developing the exposed-emulsion layer-with -a silver halide I developing solution containingsaid develop as-i ssntanc wa h n th r s l n lka o le y image u 9511 em lsion la r b chi t r ul n siivevimage and fi in s dyeing theresidual, o p e cem- P d l as qd flr laq l h e o lay r in cont with. a rs e v aa a s .,cpnta nhs a mo em. fo s id si d e an wande in thabas dy ima w sec y l b n t th ec ivin laye 18. 'A photographic reproduction process which comp e Q PQ P a u l t o Silver l d emul ion lay cpntainiug a strongly acidic coupler compound reactive with the oxidation product of a primary aromatic amino silver halide developing agent to form a dye, said coupler having an acid group in the coupling position of itsmolecule, which group is splitoif during development of the emulsion layer withsaid' developing agent, developingthe emulsion layer-withga silver halide developing solution containingsaid-developing. agent to split ofl? said group from the*coupler, compound, ,to form said dye image and coupler image in'the layer, bleaching the resultant silver image and fixing, dyeing said coupler image with a basic dye, placing the emulsion layer in contact with a layer "containing a "mordant'for said basic dye and transferring the "basic'dye imagewise by imbibitionto the receiving 'layer. V 7

References Cited in the file of this patent UNITED STATES PATENTS 2,386,167 Murray Oct. 2, 1945 2,713,305 Yutzy et al July 19, 1955 2,756,142 Yutzy July 24, 1956 2,774,668 Rogers Dec. 18, 1956

Claims (1)

1. 4. A PHOTOGRAPHIC REPRODUCTION PROCESS WHICH COMPRISES EXPOSING A PLURALITY OF GELATINO SILVER HALIDE EMULSION LAYERS ON SEPARATE SUPPORTS EACH TO DIFFERENT PRIMARY COLOR SEPARATION IMAGES OF A COLORED SUBJECT, DEVELOPING EACH OF THE EXPOSED EMULSION LAYERS WITH A SILVER HALIDE DEVELOPING SOLUTION CONTAINING A PRIMARY AROMATIC AMINO SILVER HALIDE DEVELOPING AGENT AND A COUPLER COMPOUND REACTIVE WITH THE OXIDATION PRODUCT OF SAID DEVELOPING AGENT TO FORM A DYE IMAGE OF A SUBSTANTIALLY NONDIFFUSING DYE OF THE CLASS CONSISTING OF ACID AND BASIC DYES IN EACH EMULSION LAYER, BLEACHING THE RESULTANT SILVER IMAGE AND FIXING, DYEING EACH OF THE RESULTING DYE IMAGES WITH A DIFFUSIBLE DYE WHICH FORMS A SALT WITH SAID DYE

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