US2369171A

US2369171A - Methods of photography

Info

Publication number: US2369171A
Application number: US370195A
Authority: US
Inventors: Murray Otis Willard
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1940-12-14
Filing date: 1940-12-14
Publication date: 1945-02-13
Anticipated expiration: 1962-02-13
Also published as: GB556858A

Description

Feb.13, 1945. Q W 2,369,171

METHODS OF PHOTOGRAPHY Filed Dec. 14, 1940 Gelalin'lDye JnZermedzaTe. Clear 6ela ,tin.

Silver Hallde Layer- Base.

- GelaILMDI eIntermediate. I f I I l I I I I I SLlver hallde Layer.

Gelatin-Dye Intermediate. Bcos e.

Silver Halide +Dye1n Zermecliate.

1 Ill/l/I/l/I/l/ll,

Gelatin-Dye Jnlermediale.

Gelatin.

-- -Silver Halide Layer.

Comminuted $llver+6elafin.

Base.

silver Halide Layer.

Gelatin For Receiving Imbibilion Image. Silver Halide +Dye Intermediate. Base. Gelatin +Dye intermediate.

gwuem ho o [I H5 Willard Murray Patented Feb. 13, 1945 METHODS F PHOTOGRAPHY Otis Willard Murray, South River, N. 1., assignor,

by mesne ass cuts, 'to E. L-du-Pont de Nemom-s lb Company, 'Wllmlngton, Del., a corporation of Delaware Application December- 14, 1940, Serial No. 310,195. .11 Claims. .(Cl. 95-2) v This invention relates to photography. More particularly it relates to methods ior producing colored images and to novel elements therefor. Still more particularly it relates to the production of dye image records in layers iree from'reduc'ible silver salts and to novel elements therefor, and to the preparation'of such elements. The inven.

tionfurther relates to a method 01- making two color reflection prints and transparencies, especially paper prints.

This invention has for an .objectthe provisions of a new method of making color prints. A further object is to provide a simple and economical method of making color prints. v A further object is to provide amethod of making 'a plurality 01' color prints from single image records. A still further obiectis to provide a method of making color prints free from silver images in situ therewith. Anothenobject is to providean element which can be used for the preparation of :a two color print. A further object is to provide an element which can be used 'to produce a color print in toned and color developed images. Still v other objects are to provide methods and elements tor making color'transparencies or reflection prints which require a minimum of equipment and processing steps and to make a'general advance in the art. I

The above objects are accomplished ;by the hereinafter described invention which in its broader "aspects comprises producing (1) a colored image record in an inner layer by exposing and color forming development or color toning and (2) producing a dye image color record'in an outer layer of a color yielding element by .con tact development.

Colored image records can be produced in the immobile color developing agent in the original silver salt layer and using a solution containing a color former and other necessary developer components, (4) placing both immobile color former and developer in the original light sensitive silver s'alt layer and using a solution containing the necessary developer components.

Toned images "can be produced in the inner layer by printing a color separation record onto .10 the light sensitive inner layer, developing and fixing, and then treating the silver image with a toning bath or baths.

The outer partial color record is produced in quinoneimine dyes including indophenol, indoaniline and indoamine dyes or azomethine or azo -20. color yielding element containing a dye inter- I 35 ing out the above-described processes. In gen-r eral, they comprise (a) a base, (b) one lightseninner layer by forming a latent image in the g inner light sensitive silver salt layer and then coloring the developed image record. In color forming development procedures this can be ac.-

dyes by 'imbibltion contact with a separate photographic element bearing a color record comprised of a reducible silver salt which is preferably a bleached silver image with the outer layer of a mediate capableof lorming'the aforementioned dyes in the presence of a color forming developing solution. The respective color yielding elements and photographic elements contain aqueous solutions of one or more developer'ccmponents prior to contact with each other. The color element is preferably impregnated with an aqueous alkaline solution and the photographic elemen con- I taining the reducible silver salt image is preferably treated with an aqueous solution of an aromatic amino color developing agent containing a color coupling developing agent prior to contact with the color element.

Various types of elements can be used in carrysitive silver salt layer on the base, which may contain immobile dye components and (c) a color 40 yielding layer comprising an immobile dye comcompllshed in several ways (1) by having the two developer solution, (2) by using an immobile color former and having it uniformly distributed throughout the original light sensitive silver salt layer and a developer solution containing a color. forming developing agent, (3) by placing an components necessary for forming color, e. g, the; color former and the development agent in the ponent free from silver or reducible silver salts which is spaced from said silver salt layer so that development of the latter will not produce color coupling or dye formation in the former. In one modification, the color yielding layer is spaced from thesilver salt layer by means of a waterpermeable layer of suflicient thickness to prevent color coupling. In another modification, the de veloper oxidation products couple with dye intermediates in a separation layer which are chosen 2- v to form colorless or extremely weakly colored dyes. Suitable intermediates include l-phenyl- 4,6 diketotetrahydro pyridazine, perinaphthindone, etc. In still another embodiment an unstable color forming compound which can be destroyed with weak acids, e. g. phenol, after proo-, essing, can b used in a separatory layer, e. g..of gelatin. In a preferred embodiment, however, the light sensitive silver salt layer and the color yielding layers are placed on opposite sides of the transparent water-impermeable base.

The water-permeable layers may be thin mom-, branes or composed of water-permeable materials, e. g. cellulose derivatives such as lower alkyl ethers and highly esterified partially hydrolyzed esters of cellulose, e. g. methyl cellulose, ethyl cellulose, cellulose acetate, cellulose acetate pro Y pionate, regenerated cellulose, etc., or composed of film-forming colloids, e. g. gelatine, agar-agar,

polyglucuronic acid, deacetylated chitin, amino celluloses, zein derivatives, polyvinyl alcohol, etc., which have been hardened if necessary so that they are cold water insoluble, but are water per meable.

The film base may be made of various materials, including cellulose derivatives, e. g. nitrocellulose, cellulose acetate, cellulose acetate propionate, synthetic 'rlesin's,'e. g. polyvinyl chloride,

polyvinyl alcohol and polyvinyl acetal, and super polymers-such a's ethylene and isobutylen'e polymers and superpolyamides, e. g. nylon.

Color yielding layers oftwo general types constitute useful aspects of the invention. They may thus be (1) composed of an immobile dyeintermediate uniformly distributed or dispersed in a water-permeable binding or supporting agent, and (2) composed of film forming synthetic resins containing nuclei capable of forming a quinoneimine or azomethine or azo dye on color forming development. The aforementioned reversible. colloids are useful binding agents.

In the accompanying drawing which will make the invention 'more easily understood, similar reference numerals refer to similar parts throughout the several views. 7

Fig. 1 is a schematic cross-sectional view of a film element useful for contact development and toning or color development procedures,

Fig. 2 is a schematic cross-sectional view of a modified film element useful for contact development and toning or color development procedures,

Fig. 3 is a schematic cross-sectional view of a photographic element for, contact development with an element similar to that of Fig. 2, but containing a color former in the silver salt layer.

Fig. 4 a schematic cross-sectional view of aand then with a gelatino-silver-halide emulsion to form a layer 2. On layer 2 is coated an aqueous gelatin dispersion to form a clear separation layer 3 which is substantially thicker than layer 2. On layer 3 is coated a gelatin dispersion containing at least one immobile dye intermediate to form layer 4, which layer yields a dye image by the procedures described below or composite dye image. The gelatin dispersion can be made by dissolving the dye intermediate in 5 to 10% caustic alkali to form a soluble paste. This may be diluted with about 5 parts of water and 1 part of alcohol, added to 5% aqueous gelatin and the excess alkali neutralized with a mineral acid such as hydrochloric. The concentration of the coating compositions, temperatures and coating speeds are adjusted to yield the desired thickness.

In Fig. 2, a subbed, transparent cellulose acetate film base I is coated on one side with a gelatinfsilverhalide emulsion to form a thin layer 2'. On the other side of the base is coated a gelatin dispersion to form a layer 3' which contains at least one immobile color former so that said'layer will yield a dye image or mixed dye images.

In, Figure 3 a thin film base I composed of a .fusiblesuper polymer of the type set forth in. :U. S. patents, 2,216,735 and 2,216,736, was coated on one side. with anaqueous alkaline gelatin dispersion containing a blue-green immobile dyestuff component to'form a thin layer 2".

I 7 EXAMPLE I A color yielding element of the type shown in Fig. 1 having layer 4 composed of gelatin containing 0.25 part of the o-sulfobenzaldehyde dimer of 1-(m-octadecoylaminophenyl) -3- methyl-5-pyrazolone was exposed to a printing light passing through the red separation negative of a tri-pack color-film combination. The color yielding element wasthen developed in a solution of the following composition:

, Parts 4-chloro-o-phenyl-phenol 2 N-diethyl-p-phenylenediamine hydrochloride 2 NazCOs a 20 Sodium sulfite 1 H2O to 1,000

then treated with Farmer's reducer and washed.

A' positive film was printed from the greennegative record of the tripack combination, de-

veloped, fixed and washed. It was bleached in an aqueous solution of alkaline potassium ferricyanide to form silver, ferrocyanide images,

' washed thoroughly and soaked in 10% NazCOz. The color yielding element was soaked in a solution of the'following composition: 7 N-diethyl-p-phenylene diamine hydrochloride grams 10 NazSOs do 2 Metol do 6 Water to cubic centimeters 1,000

The bleached positive was then squeegeed in register contact with the color yielding element, with EXAMPLE II A color yielding element ofthe type shown in Fig. 1 containing as the blue-green color former in layer 4 a salicylaldehyde-o-sulfobenzaldehyde atom-171 polyvinyl acetal was exposedto a printing light from the blue-green record of bi-packcolor separation negatives, developed, fixed and washed.

The element was then treated in, a toning bath.

of the following composition:

Uranium nitrate grams Potassium oxalate do 5 Potassium ferricyanide do.. Ammonium alum do 12 H01 (100 cc. conc./liter,H-z0) cc Water to 0(:

whereby an orange-fed color image record was formed in layer 2. The element was washed and soaked in a bath of the type set'forth in Example I.

The orange-red bi-pack record was printed onto positive film stock. The latter was de-..

veloped, fixed, bleached t silver ierrocyanide, washed, soaked in 10% aqueous sodium carbonate, and the emulsion surface pressed'into contact with layer 4 with the images in register until a blue-green image formed'in layer 4. Upon removal of the positive film,-a 2-color print was formed.

Exam'ta III N-diethyl-p-phenylene diamine hydrochloride ams Sodium sulfito dn 2 Metol do 0.6 Water t 7 ters" 1 NazCOz -grams 30 fixed, washed, and soaked in 10% sodium carbonate. A'positive from the blue-green bi-pack combination was bleached to formsilver ferrocyanide images, washed, soaked in alkali solution and squeegeed with the color yielding element after the manner set forth in Example L-yielding a color transparency having particularly good color rendition. r I

EXAMPLE IV A color yielding element of the type shown in a Fig. 2 containing in layer 3' as a blue-green color former the arylide of l-hydroxy-Z-naphthoic acid with p-dodeeylanilide was exposed to printing light from an orange-red bi-pack color separation negative, developed and fixed. V The silver image record was then bleached by floating on a bath of the composition:

Potassium dichromate grams 2. 25

The element wasbatlied in hypo, washed and immersed in a dye bath containing 2.13 gramsoi' (C. I. #151) of Wool OrangeA the formula and 1.54 time or SerichromeIBlue R o; I. so)

, of the formula per liter of solution to form orange-red dye images which were washed thoroughly. The outer layer was then treatedilby contact development after the manner :01 Example III to form a blue-green ye record therein. a 1

, EXAMPLE V A color yielding element of the typeshown in Fig. 3 containingin layer 2";resorcinol-monooctadecyletheras a blue-green .dye intermediate and in layerg3" a mixture ofthedye intermediates of Example III as orange-red dyezintermediates. ,An orange-red color separation negative was printed onto layer Z". which was developed in an ordinary positive typemetol-hydroquinone developenfixed, washed. bleached with Potassium bromide do. 20 Copper sulfate :10 18 Chrom alu d 3 Acetic acid cubic centime'ters-- 3.5 Water to l ers..- 2

alkaline ferricyanide, washed and treated with a dye-generating reducer such as Bath C (hereinafter described) for 3 minutes, then bleached, fixed and washed. The blueegreen color separation negative was printed onto a positive film stock which was developed. and fixed and then bleached to silver ferrocyanide images, 3. soaked in a 2% aqueous solution or N aOH and the emulsion pressed into contact with layer 3 which had previously been soaked in an aqueous solution of the following formula: V,

Monophenylhydrazine 2 2% aqueous sodium o1eate 5 Sodium carbonate 2 The elements were squeegeed in register until a dye image in the outer layer, whereupon the elements were separated, washed and mounted on a paper base. A two-color print of good strength, color rendition and improved resistance to fading was obtained by the above of v film element and process.

EXAMPLE VI An element of the typeset forth in Example r v, but containing in layer ,3 in addition to the dye intermediate, about 2 parts of p-amino-N-dicombination ethylaniline per part of color-former, was made.-

The layer 2' was processed after the manner set forth in Example IV. A bleached positive was also made in a similar manner andplaced in contact with the layer 3' which had been pre-- viously soaked in an aqueous bath containing 30 cos. of hexamethylene diamine-LG per liter of solution and squeegeed until a color image'appeared in said layer.

EXAMPLE A color yielding element of the type shownin Figure 4 comprises a transparent support (1) coated on one side with an ordinary positive-type silver bromide emulsion'i. On'the other side of the transparent support is a thin layer 8 or comminuted silver dispersed in gelatine so as to form a light-barrier layer of metallic silver having a density such that less than 1% of the light is transmitted by the layer; On the'light-barrier layer is coated asilverhalide: emulsion layer 1 7 containing 4 :4-bis:-(3' '-methylpyrazolonyl-1 biphenyloxide. On the silver halide layer con-- taming-the magenta color iormer'is coated a layer 8 oiclear gelatine and over this a layer9 of gels.- tine containing parts of diacetoacet-tolidme sulioneper 100' parts or gelatine. A positive type negatives, the green record was printed onto the 7 silver halide" layer and the entire him was then developed in a p-amino-N-diethylaniline-Metol" silver bromide emulsion coated on an. aluminum,

, toil supportprepared as described in Mason j 2,115,339 was printed from the blue separation negative, developed in an ordinary black and alkaline "ferricyanid'e.

silver halide emulsion layer. yielding unit was then immersed in an ordinary black. and white positive type of developer to develop-the latent images in. both of the. exposed silver halide layers, After development, the film 'unit was washed. :The inner silver image was, thentoned mage'ntaby treating. it first with a solution comprised of l liter of a solution containing 5% nickel nitrate and of potassium citrate with 50. cc olf a 4% solution of potassium ferricyanide and 5 cc.- of 10% nitric acid. The

bleaching was done by floating the side of the film same side in a solution comprising:

Parts 5 carrying the gelatine and dye-intermediate and silver halide layers on the surface of the bleaching solution for approximately 6 minutes and then washing the entire film and then floating the chloride "grams" 10' NazSOa V 2. v Metol s A saturated solution of dimethylglyoxime 50 water m 0.4% sodium hydroxide; 50 4 and then squeegeed into contact with the bleached Water.- -1 400 (All parts by volume) I after which the film .was rinsedfor two minutes.

I The rear sidewas then floated on an alkaline ferricyanide bleach bath washed and redeveloped in a blue-green color forming developer similar to that described under Example-I. After the final development, the blue-greenlayer was floated on an alkaline ferricyanidebleach bath, washed and the entire film was then immersedin a 5% plain hypo solution and given the final washing. After washing, the color element was immersed in a colordeveloper as, described under Example III and squeegeed into contact with the bleached positive image on the metallic foil base which had first been saturated with a.10% sodium carbonate solution, and leftin contact until the yellow dye image was produced in the outer layer, after .Figure 5 comprises a transparent support I. coated on the one side witha gelatine layer l0 contain- .irig approximately 1 gram of 2-hydroxy-3-methyl benzaldehyde phthalaldehydic acetal of polyvinyl alcohol per 4 grams of gelatine. On the other side of the transparent support is coated a silver halide. emulsion layer ll containing approximately 6 grams of l-(m-octadecoyl-amino-phenyl-3-methyl-5-pyrazolone) .per 1000 grams of emulsion. Over the magenta. yielding layer is coated a layer I! of' plain gelatine from an 8% aqueous, dispersion. Using 3-color separation developer as described under Example I. The ele- -rnent was then treated with Farmer's reducer to remove the metallic silver and undeveloped silver halides from the inner layer. The red color separation negative was printed onto a positive silver halide emulsion on the aluminum oxide surface of aluminum foil prepared as described in Mason,

U. S. Patent 2,115,339. The red record positive was developed in an ordinary metol-hydroquinone developer, fixed, washed and bleached with alkaline ferricyanide solution. A positive matrix was prepared from the blue separation negative by printing through the base of a film coated with a positive-type silver bromide emulsion, developing it in a pyro developer containing a minimum of snlfite, (to harden the gelatine in situ with the silver image), fixing and washing in warm-water to remove the unhardened gelatine. or course, any of the other well-known methods for forming matrices can also be used, (for example, see History of Three Color Photography, by E. J. Wall).- The silver image was then removed by treatment with alkaline ferricyanide and sodium thiosulfate. A yellow imbibition image and a blue-greencolor-developed dye image were then this element in the following manner: The bleached positive from the red separation negative was saturated with 10% sodium carbonate solution and the blue-green dye component layer was it floated on a developer comprising: p-Amino-N-diethylaniline hydroimage on the aluminum foil support. While this contact development was in progress, the upper clear gelatinelayer was saturated with a 1% aqueous solution of silver nitrate and the matrix on the transparent base was soaked in a 10%- potassium iodide solution and then squeege'ed into registered contact with the clear gelatine layer forming therein a silver iodide image which is an excellent mordant for basic dyes. The matrix was then removed and a'yellow dye fixed on the ,Jgto the two outer layers are then removed, the

ill-m isv cleared in plain hypo, and washed, yielding a brilliant three-color transparency comprised of a metallo-organic image, a color-developed image and a mordanted dye image.

The invention is not limited to the exact procedures and materials, compounds or elements set forth in the above examples. On the contrary, a wide variety of color yielding elements, dye components or color formers, developing agentsand solutions, toning baths, dye mordants, coupling baths, can be substituted with similar results.

The color yielding elements may contain light sensitive layers composed of simple or mixed silver halides which may contain the usual sensitizers, desensitizers, stabilizers, fog inhibitors,

emulsion hardeners, etc. Suitable types include silver chloride, silver bromide, silver chlorobro-' mide, silver chloride-bromide-iodide, silver broformed respectively in the two outside layers of I mide-iodide, etc., which may contain cyanine, carbocyanine, polymethine cyanine, cyazine, carbocyazine, pseudocyanine, kryptocyanine, merocyanine, rhodanine, etc. salts and bases. The silver halide layers are anchored to the supports by means of the usual subbing solutions. Such solutions are also useful for anchoring dye component layers to bases.

While the above description has been restricted for the most part to the formation of dye images in non-photographic layers by bringing a separate element containing reducible silver salt images into contact with the dye-yielding layer in the presence of the constituents of a colorcoupling developer, it is also possible to form such dye images by separate elements containing images other than silver salt images. For instance, one may employ the reducing action of chromium oxides formed by exposing bichromated gelatine layers. For preparing such images, a film support is coated with a thin gelatine layer, sensitized for example, by bathing in an alkaline bichromate solution, dried and exposed under a negative to a printing light containing some ultra-violet radiations. The exposed film element is then soaked in alkali and pressed into contact with the color yielding element which has been saturated with a color coudodecoylamino-phenyl) -5 pyrazolone, 4,4 bis- (3-methyl pyrazolonyl-l") -diphenyl (described in Jennings and Middleton, U. S. P. 2,200,924), 4,4'- methylene bis -(m stearoylaminophenyl) methyl pyrazolone, U. S. P. 2,294,909, and 4,4'-osulfo-benzylidene-bis (phenyl methyl pyrazo- 7 lone), U. S. P. 2,294,909.

pling developing solution. In'fact, each of the above described procedures for imbibition or contact development can be used with the elements containing other types of developable images.

The procedures and compositions for forming colored or dye images set forth in U. S. Patent No. 2,328,034 of O. W. Murray and V. B. Sease, entitled Photographic elements and processes, can be used in the procedures hereof.

The dye components or color formers are in general selected so that they together form a composite dye image which reproduces a color scene or object. Thus, the dye components used in the layer which is treated by contact development in general should form dyes complementary in color to that which exposed the color separation negative record employed therewith. Likewise, the dye components or color formers used in the inner layer or the developing solution used for processing thereof should form a dye which is complementary in color to that which exposed the color separation record. However, the above general considerations are not true when it is desirable to print a negative color record from a negative color record or a positive color record from a positive color record. When reproduction of an original color object field is not a desideratum, a dye which forms any desired color can be used.

" ethyl) As examples of suitable yellow color formers Suitable non-migratory blue-green color formers of especial utility include 4,4-di-(1-hydroxy- 2-naphthoylamino) diphenyl, 1-hydroxy-2-carboxy-5-dodecoylamino naphthalene, l-N-steroyl- 4-N-(1'-oxy-2' naphthoyl) phenylenediamine sodium sulfonate, resorcinol mono-n-dodecyl ether (described in Salzberg & White U. S. Patent No. 2,166,181 (filed September 21, 1937), product of p-hydroxybenzoic acid and formaldehyde (described in McQueen, Serial No. 261,794, filed March 14, 1939, now U. S. P. 2,323,481), product of polyvinyl alcohol and salicylaldehyde (described in Dorough & McQueen, Serial No. 233,480, filed October 5, 1938, now U. S. P. 2,310,943).

Additional color formers which are useful not only with arylene diamino developing agents, but also the aryl-hydrazines, are described in U. S. Patents, 2,154,918, 2,166,181, 2,178,612, 2,179,228, 2,179,238, 2,179,239 2,213,986, 2,179,244, 2,186,045, 2,186,719, 2,186,734, 2,186,735, 2,186,736, 2,186,849. 2,140,540, 2,133,937 and 2,200,924, etc. Others are set forth in the Seas'e-Murray application filed on an even date herewith, and may be substituted for the dye intermediates of the above examples in accordance with the teachings hereof.-

The preferred'developing agents which may be used in the dye coupling development steps hereof are derivatives of p-phenylenediamine and particularly the asymmetric dialkyl p-phenylenediamines of 1 to 4 carbon atoms, e. g. p-aminodimethylaniline, p-aminodiethylaniline, p-aminodibutylaniline, etc. Other developing agents which maybe used include p-phenylenediamine itself, p-methylaminoaniline, p-ethylaminoaniline, p-aminophenol, N,N-diethyl-o-phenylenediamine, chloro-p-phenylenediamine, 1,2,5-toluylenediamine, 2-amino-5-diethylamino-toluene, p-

amino-Nphenylmorpholine, N-p-aminophenylpiperidlne, N-methyl-N-hydroxyethyl-p-phenylenediamine, N-butyl-N-hydroxyethyl-p-phenylenediamine, 2-amino-5-(N-butyl N hydroxy aminotoluene, fi-v-dihydroxypropyl-pphenylenediamine, etc. These aromatic aminodeveloping agents in the form of their organic or inorganic acid salts may be used in the preparation of the developing solutions. The salts are in. general more stable than the free bases. As examples of suitable salts, mention is made of the hydrochloride, sulfates, acetates, etc.

In addition to the developing agents as aforedescribed the developing solutions may contain from about 3 to 30 parts of an organic nitrogen base having an association exponent of atleast 5.0 to about 11.40 including aliphatic amines, primary, secondary and tertiary alkyl monoand poly-amines, cycloaliphatic amines, ammonium hydroxides, ammonia, N-heterocyclic amines, etc. per 1000 parts of solution. Suitable bases are described in the following solutions which can be used as described above. The bases can be used in water alone as described in Example V.

Bath A ri-Amino-N-diethylaniline grams 2 Ammonium hydroxide, conc.

cubic centimeters-.. 25 Sodium sulfite, anhy grams- 2 Water to liters 1 Both B p-Aminodiethylaniline g'rams-- 2 Hexamethylenediamine (55% in methanol) cubic centimeters Sodium sulfite, anhy grams 3 Water to 7 up.

Bath c I p-Aminodiethylaniline grams 3 Ammonium hydroxide, conc.

cubic centimeters-.. 30

Sodium carbonate, anhy grams- 2 Water to liters.. 1

. Bath-D p-Amlnodiethylaniline -grams 3 B-dimethylaminoethylamine cubic centimeters- I Sodium sulfite, anhy "grams" 3 Water liters 1 Bath E p-Aminodiethylaniline grams 2 Piperidine cubic centimeters Sodium sulflte, anhy... "grams... 2 Water to liters..- 1

Bath F 2-Amino-5-diethylamino-toluenegrams 5 Trimethyl-benzyl-ammonium hydroxide cubic centimeters-.. 20

Sodium sulflte, anhy grams 5 Water to liters 1 Bath G 4:4-diaminodiphenylamine "grams" 4 Hexamethylenediamina--cubic centimeters 10 Sodium sulfite, anhy grams 2 water tn liters 1 Bath H 1 zi-dlaminonaphthalene "grams" 3 Dimethylcyclohexylamine-cubic centimeters Sodium sulflte, anhy .;..grams 3 Water to liters 1 Bath I 4-Diethylamino-i-naphthylamine grams 5 B-dimethylaminoethylamine In place of the specific hydrazines set forth in Example IV may be substituted other hydrazines such as 0-, mor p-tolylhydrazine, p-nitrophenylhydrazine, p-hydrazinodiphenyl, p-bromophenylhydrazine, chiorophenyl hydrazines, chloronaphthyl hydrazines, bromonaphthylhydrazines, pdiphenylhydrazines, p,p'.-diphenyldihydrazines, p,p'-diphenyldihydrazines, alpha-naphthylhy. drazines, beta-naphthylhydrazines which may be Potassium ferricyanide --grams 12.5 Uranium nitrate d0 12.5 Rose bengal do- 0.013 Naphthol yellow do.. 0.012 Iodine do 0.013 Glacial acetic acid.. cubic centimeters" 12.5 Water to do 1,000

Toning bath B (minus blue) Vanadium oxalate solution .7 cubic centimeters Oxalic acid (set) ..do- 50 Glycerin do 50 Water to do 1,000

employed in the form of their salts, e. g. hydrochloride, acetate, chloroacetate, sulfates, etc. The hydrazines may be solubilized by means of long chain aliphatic carboxylic acid salts and long chain aliphatic sulionic acid salts as set forth in Kirby application, U. S. P. 2,220,929.

In the case of elements which contain film forming color formers as the outer layers, no additional binding agents such as gelatin need be present. .Color formers oi this type which are especially suitable are (1) polyvinyl acetals of aromatic aldehydes which are capable of reacting with diazo compounds and the oxidation products of photographic color developers. The acetals are formed irom polyvinyl alcohol or partially hydrolyzed polyvinyl esters and aromatic aldehydes which contain a phenolic hydroxyl, amino, alkyl-, cycloalkyl-, or arylsubstituted amino group including mixed groups of this typ which are further characterized in that they have a reactive position, but not necessarily unoccupied position, ortho or para to the mentioned groups or the aromatic aldehydes having an active methylene group. The preparation of suitable compounds of this type is set forth in U. S. P. 2,310,943 and (2) condensation products of phenols and naphthols or hydroxy aromatic carboxylicor sulfonic acids with difunctional resiniorming reagents such as aldehydes and ketones, dimethylol derivatives of phenols, amides and amines and equivalent compounds. The preparation of suitable color formers of this type is described in U. S. P. 2,323,481.

Various other toning baths and procedures may be substituted for the specific one set forth in Example II. Additional onesinclude:

Toning bath A (red) For use add 1 part 5% KFewNM to parts of above solution and bathe silver image in it.

Toning bath C (blue) Oxalic acid grams.. 1.75 Iron ammonium oxalate ..do 4.75 Potassium ferricyanide do 1.75 Water to cubic centimeters; 1,000

Toningbmth D (blue-green) Solution A: v

Oxalic acid "grams" 20 Ferric ammonium oxalate -do.. 50 Potassium ferrlcyanide -do 20 Water to ..liters 1 Solution 3:

Ammonium vanadate ..grams 2.6 oxalic acid do 4.5 Water to cubic centimeters" 40 For use mix solutions A and 1B and add water to make '4 liters.

A number of difierent bleaching procedures can be used for the elements which are used for contact development. Films or plates containing a positive or negative silver image can be bleached to redevelopable silver salts, as for example, with potassium ferricyanide, copper chloride, or copper bromide in the presence of an oxidizing agent such as chromic acid, potassium ferricyanide in the presence of alkali carbonate or ammonia, etc.

In place of the sodium carbonate solutions may be used potassium carbonate, potassium hydroxide, lithium carbonate, and other aqueous solutions for soaking the bleached photographic elements. The concentrations may range somewhat depending on the pH of the particular agent, the bleaching agent used, the dye intermediate used and the concentration of thedeveloping agent, and amount of sulfite present. In general, amounts of 2 to are practical.-

In making the above color yielding elements, the color formers may be made into a past with alkali and brought into solution with water or alcohol and then mixed with an a ueous dispersion of a reversible colloid, e. g. gelatin, preferably containing a dispersing agent and coated onto a base having a substratum of the type suitable for anchoring silverhalide layers, The same types of coating procedures used for silver halide emulsion layers have been found satisfactory. In the case of film forming color formers, the alkaline aqueous or alcoholic solutions may be cast in a smiilar manner. 8 I

For the production of color prints and transparencies from strip or continuous film, e. a. colored cine prints or transparencies, the dye images can be prepared in the same general manner as previously described. The color yielding should in general have the same shape as the photographic element. Intimate contact may be maintained between the color element and the bleached element by running the elements in intimate contact after they have been suitably treated for color coupling through pressure rolls or down a belt until color coupling and the formation of dye images has been completed.

The pressure rolls and belts are preferably provided with sprockets which fit into perforations in the color yielding elements and photographic elements to insure accurate registration of images if they are mounted in registration with other color component records, e. gfrom color separation negatives. However, even in the case of single color elements, the sprockets and perforations insure against slipping with the resultant production of fuzzy dye images records.

It will be apparent from the above that th s invention is of wide utility and has a number of decided advantages.

A major advantage resides in the fact that twocolor prints can be made in a simple and economical manner. A further advantage resides in the fact that a number of tedious steps are eliminated from prior processes of making two color prints. A still further advantage resides in the fact that the color development of one layer can be conducted under ordinary illumination which permits accurate registration of'color records to be made.

As many apparently widely different embodiments of this invention may be madewithout departing from the spirit and scope thereof it is to be understood that I do not limit'myself to the specific embodiments herein except as defined by the appended claims.

I claim:

1. The process which comprises printing one of two color separation records onto the light sensitive layer of a photographic element comprising a transparent base having a light sensitive silver halide layer containing an immobile color former on one side of the base and a light insensitive colloid layer containing an immobile color former on the other side of the base, one of said color formers being capable of forming a blue green and the other an orange red, dye, color developing the latent image and fixin the same, bleaching the second record and forming a dye image in the colloid layer of said element by placing said record in register and squeegeeing it with said element while subjecting said record and element to the action of a color coupling developing agent.

7 2. The process which comprises printing one of two color separation records on to the light sensitive layer of a photographic element comprising a transparent base having a light sensitive silver halide layer containing an immobile dyestufl. in-

, termediate capable of color coupling development I coupling, developing agent, placing the bleached record in register with the color developed images on one side and a lightinsensitive colloid layer containing adiflerent immobile dyestuii intermediate capable of color coupling development on the other side of the base, color developing the latent image and fixing same, bleaching the second record, impregnating the bleached record in -an alkaline aqueous solution, impregnating the light insensitive layer of the color yielding element with a reducing solution containing a color on the light insensitive layer and squeegeeing it with said element while subjecting said record and element to the action of a color coupling developing agent.

3. The method of producing a color photograph which comprises forming in a color yielding element having a light sensitive silver salt layer and an outer light insensitive layer containing a dye'intermediate capable of color coupling development, by printing one color component image record therein, developing the latent image formed and forming color in the image areas of the light sensitive layer; producing in-the light insensitive layer another coactive color component image record by impregnating said layer with an aqueous solution, impregnating a sepa rate photographic element containing such coactive color record in the form of reducible silver salts in an outer layer thereof with an aqueous ment having a light sensitive silver salt layer and i an outer light insensitive layer containing an immobile dye intermediate capable of color coupling development, by printing one color component image record therein, developing the latent image formed and forming color in the image areas of the light sensitive layer; producing in the light insensitive layer another coactive color component image record by impregnating said layer with an aqueous reducing solution containing a primary aromatic amino color developing agent, impregnating a separate photographic element containing-such coactive color component record in the form of reducible silver salts in an outer layer thereof with an alkaline aqueous solution, and pressing said impregnated layers into contact until a dye image is formed in the outer layer of the color yielding element.

5. The process of making a two color photograph from two separate color component images in the form of silver images, one of which is a positive image of a coactive color component image record and is located in the outer layer of a photographic element and the other a negative image of a coactive color component image record, which comprises printing the negative image record onto a color yielding element having a light sensitive silver halide layer and a separate outer color yielding light insensitive layer containing an immobile dye intermediate capable of color coupling development, developing the latent images formed and coloring the images developed to depict the color of aforesaid record, bleaching the positive color component image record-and impregnating the element bearing it with an alkaline aqueous solution, impregnating said light insensitive layer with an aqueous solution containing a color forming developing agent and pressing said impregnated layers into contact with th images in register until a dye image is formed in the outerlayer of the color yielding element.

6. The process as set forth in claim wherein said latent image is converted into a dye image by color coupling development of said latent image.

7. The process as set forth in claim 5 wherein the latent image is converted into a color image by color toning said latent image.

8. The process as set forth in claim 5 wherein the latent image is converted into a color image by dye mordanting of said latent image.

9. The process which comprises forming a color photograph in an element comprising a transparent base having a light sensitive silver halide layer on one side thereof and in order on the other side thereof a comminuted silver-colloid Patent No. 2,569,171.

CERTIFICATE OF CORRECTION.

OTIS WILLARD llIlRRAY.

opment, by printing color component image records onto said light sensitive layers from opposite sides of the base and developing said layers with a color coupling developing agent, bleaching a separate photographic element containing a coactive color component image record in the form of a silver image in an outer layer thereof, impregnating said latter layer with an aqueous solution containing a primary aromatic amino color developing agent, impregnating said color yielding layer with an alkaline aqueous solution, placing said impregnated layers in register, and pressing the same into contact until a dye image forms in the color-yielding layer.

10. The process which comprises printing one of two color separation records onto the light sensitive layer of a photographic element comprising a transparent base having a light sensitive silver halide layer and a stratum of immobile dyestuff intermediate capable of color coupling development on one side thereof and a light insensitive cblloid layer comprising essentially a difierent immobile dyestuff intermediate capable of color coupling development on the other side of the base, color. developing the latent image and fixing the same, bleaching the second record and forming a dye image in the said light insensitive colloid layer of said element by placing said record in register and squeegeeing it with said element while subjecting said record and element to the action of a color coupling developing agent. 11. The process which comprises printing one of two color separation records onto the light sensitive layer of a photographic element comprising a transparent base having a light sensitive silver halide layer and a stratum of an immobile color former on one'side thereof and a light insensitive colloid layer comprising essentially an immobile color former on the'other side of the base, color developing the latent image and fixing the same, bleaching the second record and forming a dye image in the said light insensitive colloid layer of said element by placing said record in register and squeegeeing it with .said element while subjecting said record and element to the action of a color coupling developing agent.

OTIS W. MURRAY.

February 15 11914.5.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, sec- 0nd column, i L 9, after "image" "insert -formed-- {p ge 5,:second column, line 714 and page 6, first column, lines 6, 12,19, 25, 52, 58, 11.5, 50, 57 and 6h respecti fely, after "anhy" insert a periodyandsecond column,

line l e, for "0.012" read --o.o15-'- should be read with this correction therein that the same may conform to the record of the case in the Patent Office. I Q Signed and sealed this 12th day of June, A. D. 1915.

(Seal) Leslie Frazer Acting Commissioner of Patents.