US2328034A - Photographic element and process - Google Patents

Description

u ow Aug. 31, 1943. v. B. SEASE EI'AL 2,328,034

PHOTOGRAPHIC ELEMENT AND PROCESS Filed" Dec. 14, 1940 1 Immqbi/e Dye Intermediate.

, jg E.

2 Film Formin D e ./A//%/-/;7Zl 9 Transparent Base.

GelaTin and Immobl'le Dye Intermediate. 1 Transparent Membrane. Adhesive- 1 Transparent Base.

III/1 Pressure 1 1 1 1 1 1 1 Base. 1

Bleached Silver Image. 4' p Ge/aTin andfmmobi/EDge x A w Intermediatg. /"1 1 I 1 I )1 1 r 1 1 I g/av/flca fi/fi }Tq;;;; P f/embme T T I T T T T Transparent Base. mg .7-

Maqenla. ]nm 2 Component. Green Image omponent. Yellow Image Component. Paper Base.

Virgil 15.52352 UTi5W.MurI'a L| Rie-genrated. Cellulose and I Patented Aug. 1943 PHOTOGRAPHIC ELEMENT AND PROCESS Virgil B. Sease, New Brunswick, and Otis Willard Murray, South River, N. J., assignors, by mesnc assignments, to E. I. du Pont de Nemours &

' Company, Wilmington ware , Del., a corporation of Application December 14,1940, Serial No. 370,194

This invention relates to a novel process of color photography. More particularly it relates to a novel process of producing color prints. Still more particularly it relates toa process for producing multicolor prints. ,Still'gmore particularly it relates to a process for producing dye images in films or plates which are tree from light'or radiation sensitive layers or strata, especially silversalt layers, or strata. The invention also relates to novel color.v elements for use in aforedescribed processes and tothe preparation of such elements.

This invention has for an of.a new process oi making'color prints. A further object is to provide a method of making color prints which involves economical elements and processing baths; A still further object is to provide a process for making multicolor prints which involves a, few simple processing steps.

Another object is to provide a processfor making color prints which requires simple and economical equipment. Another object is to provide novel elements for making color prints which can be successfully processed by-a few simple steps. A further object is to v provide novel elements in whichcolored images can be produced. Still other objects are to provide stable light insensitlve elements for making color prints and to make a general advance in the art.

The above objects may be accomplished by obiect the provision- 13 Claims. (01. 95-2) three color separation negatives can be bleached in a similar manner, then contacted with three separate color yielding elements containing dye intermediates of the afore-described types which are capable of forming three separate colored dye images, e. g. yellow, blue-green, and magenta. The color elements-are then superposed in register, preferably to form a color print or color transparency. v

Various types of color elements may be made and used in accordance with the teachings hereof. One practical type comprises a water impermeable base member having superposed thereon a' water-permeable layer or stratum free from light sensitive salts or materials comprising a dye intermediate capable of forming a quinoneimine dye including indophenol; indoaniline and indamine dyes, an azomethine dye or an azo dye by color' forming development, e.' g. with an arylenediamino developing'agent, or a hydrazine developing agent. The dye intermediate layer or strata may be of two general types (1) composed of a dye intermediate or color former uniformly distributed or dispersed in a water-permeable binding or supporting agent, and (2) composed of film forming material containing within its the inventions which are hereinafter described and illustrated in the accompanying drawing.

In its broader aspects a color yielding element which comprises a water permeable stratum or layer containing -a dyestuff component capable of forming a quinoneimine, azomethine or "azo dye upon color forming development is contacted with a. separate element bearing a reducible silver salt or bleached silver image in the presence of a color forming developing agent. The respective color elements and photographic element are saturated with aqueous solutions prior to contact with each other. The color element is.

preferably saturated with an aqueous alkaline solution and the photographic element bearing the silver salt image is preferably saturated with an aqueous color forming developer solution prior to contact development. The contact development is allowed to proceed until a colored or dye image is formed in the color element. The two elements are then separated. The photographic element containing the silver salt image may be contacted successively with a plurality of color image elements after bleaching between each. contact development. Positives printed from structure dye forming nuclei, i. e. nuclei capable of forming a quinoneimine, azomethine or azo dye on color forming development. Gelatin, agar-agar, gum arabic, partially saponified poly- .merized vinyl acetate, gliadin, amino-cellulose salts, etc., form useful binding agents.

The support of the above elements may be transparent and quite thin so long as they possess suilicient mechanical strength for processing and handling, or they may be adhesively joined to a paper or transparent support of greater strength and/or thickness and/or to a thin membrane or support.

Another practical type comprises an element composed of water permeable transparent ma-' terial having uniformly dispersed therein or distributed therethrough, dye intermediates of types (1) or (2) as above described; Such elements should be of a thickness and possess a wet strength suflicient to enable it to be processed, e. g. color developed in the above manner and washed and dried or transferred to a permanent support. Suitable materials include cellulose derivatives such as ethers, e. g. ethyl, methyl and benzyl ethers, etc.; cellulose simple and mixed 'esters, e. g. acetate, propionate, acetate-propionate; ethers with glycollic acid and its salts, etc., regenerated cellulose resins, e. g. hardened polyvinyl alcohol including partially hydrolyzed simple or mixed polyvinyl esters of organic or inorganic acids such asthe chloride, acetate, etc.,

a-hydrocarbon substituted acrylic acid esters, Y

.-etc., e. g. methyl methacrylate, various acetals of polyvinyl alcoholderived from aldol, glyoxal and formaldehyde and containing suitable plasticizers, etc.

Still another type of color element comprises a water-permeable colloid layer or stratum having uniformly dispersed therein an immobile dye intermediate of aforesaid type and an aromatic polyamine containing at least one unsubstituted amino group. A small amount of an alkaline sulflte, for instance, sodium suliite in an amount equal to about 0.5% by weight of the developing agent, may be incorporated in the layer. This element may be processed in a similar manner but it is not necessary to have an aromatic amino developing agent in the developer solution The color elements just described may contain more than one color yielding stratum on a single base in a single element. Thus, two diiferent color yielding layers can be mounted on opposite sides of a single transparent support composed of water impermeable material. The immobile dye components in the respective stratum should yield different colored dye images in order to obtain a multicolor picture. In an alternative form;

two color elements may be placed on each side of a transparent base composed of water-permeable material of about 0.005 inch thickness.

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

Fig. l is a cross-sectional view of a simple color element.

Fig. 2 is a cross-sectional view of a modified single color element.

Fig. 3 is a cross-sectional view of a further modified single color element.

Fig. 4 is a cross-sectional view of a further modified single color element.

Fig. 5 is a cross-sectional view of a stripping single color element.

Fig. 6 is a cross-sectional view of a photographic element bearing a bleached silver halide image in contact with a stripping single color element during contact development.

Fig. 'l is a schematic cross-sectional view of a 3-color print made by contact development of color elements of the type shown in Fig. 1.

The single color element of Fig. 1 which is useful for the production of single color or composite prints, e. g. 3-color prints, comprises a filmcomposed of cold water-insoluble water-permeable material such as a. cellulose derivative such as lower alkyl ethers and highly estez'ified esters of cellulose, e. g. methyl cellulose, ethyl celluose, cellulose acetate, cellulose acetate propionate, regenerated cellulose, gelatin, agar-agar, and mixtures of these, etc., which contains an immobile dye intermediate capable of forming a quinoneimine or azomethine dye with an aromaticamino developing agent uniformly distributed therethrough. The thickness may vary in accordance with the properties of the material used but in general should be suflicient to enable it to be processed and handled without rupture or disintegration. Various types of specific immobile dye intermediates may be used. They may contain one or a plurality of groups which will enable dye coupling or color forming development to take place.

The dye intermediates or color formers may be 7 incorporated in the binding agent before or after formation of the film I. The types which are to be dispersed in gelatin or other similar colloid binding agents may be (1) substantive to 'the gelatin or binding agent, (2) soluble in aqueous alkaline liquids but fast to diifusion when present in emulsion layers, (3) colloidal in nature so that they cannot be extracted by simple extraction from the layer by aqueous treating liquids, (4) high molecular weight so that migration through the cellular structure of, the binding agent is prevented, (5) highly insoluble, (8) film forming.

Substantivity can be strengthened by agents which have precipitating action, e. g. diphenyl guanidide, diphenylbiguanidide, etc.

The color element of Fig. 2 comprises a film 2 composed of film forming material containing within its structure dye forming nuclei, 1. e. nuclei capable of forming a quinoneimine, azomethine or azo dye on color coupling, especially color forming development. Various polymeric and resinous color formers niay be used in this embodiment. The thickness may vary considerably depending on the-specific properties of the film forming color former, but in general should be suiilcient to enable it to be processed and handled without rupture or disintegration.

According to Fig. 4 a gelatin dispersion of an immobile dye intermediate is coated on transparent film base 3 to form a thin layer 4. The

base may be composed of cellulose derivatives,

e. g.- cellulose nitrate, celluloseepropionateacetate, cellulose acetate, regenerated cellulose,

synthetic resins, e. g. polyvinyl acetals, esters, etc.,

acrylic acid esters, or superpolyamides, e. g. nylon. I

The stripping" type of color element of Fig. 5 represents an important embodiment of the in vention. It comprises a transparent base 3 to which is adhesively secured by layer I, a color element comprising a transparent membrane 6 which is preferably water permeable on which is coated a layer 4 comprising ,a water permeable binding agent having uniformly distributed therethroughan immobile dye intermediate of the above-described types.

Various materials may be used for the mem- I branes which must be porous to aqueous fluids.

Suitable materials include collodion, synthetic resins, e. g. polyvinyl esters such as partially hydrolyzed polymerized vinyl acetate; polyvinyl acetals which are the condensation products of partially or completely hydrolyzed polyvinyl acetate and an aldehyde such as formaldehyde,

r acetaldehyde or butyraldehyde, alkyd resins, i. e..

condensation products of polybasic acid compounds and polyhydroxyl alcohols, e. g. from phthalic, adipic, succinic, maleic, fumaric, etc. acids and anhydrides with glycerol, ethylene glycol, diethylene glycol, ipentaerythritol, sorbitol, etc., nylon, i. e. film forming amide polymers (see U. S. Patents 2,071,250, 2,071,253, 2,130,948 and 2,141,169); etc. i

' The adhesive layer I can be composed of watersoluble or water-swellable adhesives which have been used in prior art stripping films. A large. number of materials which are suitable for the adhesive strata or layers are readily available and may be used in making the novel stripping elements hereof. Water soluble, or alkali soluble cellulose derivatives, e. g. methylcellulose, ethylcellulose, cellulose acetic acid'or cellulose glycollic acid and its water soluble salts, suchas alkali metal, ammonium and amine salts; water soluble starch derivatives, e. g. starch glycollic acid and its water soluble salts; water or alkali soluble resins, e. g. polyvinyl alcohol, polyvinyl vinyl esters, e. g. formates, etc., alkyd resins, polyamides, water sensitive polymeric amino-nitro gencontaining bodies, insoluble in water and ammonium hydroxide, but soluble in aqueous acetic acid of concentrations in the range of float away from the temporary support in de- Suitable specific materials are deacetylated chitin, piperidylmethylzein, dicycloveloping baths.

hexylaminoethyl methacrylate, piperidy-l -N- ethyl methacrylate and mOrpholino-N-ethyl methacrylate.- Other materials of this type which may be used include the deacetylated chitin which may be prepared according to Rigby U. S. Patent 2,040,879; the acid soluble reaction products of proteins with carbonyl compounds such as'loweraliphatic aldehydes and ketones and amines having less than nine carbon atoms in which the amino-nitrogen is joined to the allphatic carbon, foroexample, those disclosed in Meigs U. S. Patent 2,143,023, January 10, 1937; the aminocelluloses soluble in dilute acetic acid and containing an amino-nitrogen removed from the cellulose nucleus bya chain of atoms comprising at least one carbon atom, for example,

those described in Hardy U. S. Patent 2,136,296; cellulose amines which are soluble in a stoichiometrical amount of 5% aqueous acetic acid containing directly attached to the cellulosic nucleus from 0.5 to 1.5 amino-nitrogens per glucose unit, these amino-nitrogens being attached to nucleus carbon atoms, for example, those in Haskins U. S.

Patent 2,136,299; reaction products of vinyl ketone polymers with amino compounds, for example, those described in Balthis U. S. Patent 2,122,707; the products obtained by treating resins having ketone groups with anexcess of ammonia or the equivalent thereof and hydrogenating the resulting mixture catalytically at superatmospheric pressure and temperature, such as those described in Greenewalt U. S. Patent 2,063,158; polymeric amino alcohol esters of acrylic and substituted acrylic acids, for example, those described in I-Iarmon'U. S. Patent 2,138,762, November 29, 1938; and the polymeric amino alcohol methacrylates described in Graves U. S. Patent 2,138,763; etc., singly or in combination. These polymeric amino-nitrogen containing substances are insoluble in" water and 5% aqueous ammonia but soluble in aqueous acetic acid of some' concentration within the range 25%. These soluble in 2% acetic acid are preferred. These. polymeric-nitrogen containing substances may be divided in several groups as follows:

1) Those which may be termed cellulose derivatives. This includes, although not with strict accuracy, deacetylated chitin and the alkylamino and amino-alkylcelluloses above-identified.

(2) The second group consists in synthetic resins in the formation of which ammonia in some instances and monomeric-amino-nitrogen.

containing bodies in other instances have been employed. This group is distinct in that the highly polymeric molecules are built up wholly by artificial means. nature. In addition to the resinous polymeric amino alcohol esters of acrylic acid or of its homologs substituted in the alpha position-by a hydrocarbon radical, there may be employed resinous reaction products of phenols, ,aldehydes and ammonia or primary or secondary amines, for example, the reactionproduct of meta-cresol, formaldehyde and dimethylamine.

(3) The third group consists of protein derivatives containing sufficient amino-nitrogen to enablethem to meet the solubility requirements of the definition above given.

The color yielding elements above described may be further modified by incorporating with the .dye intermediates or color formers various wetting agents or rewetting agents. Suitable agents of this type include the water-soluble alkali metal, ammonium, substituted ammonium and amine salts of alkyl and alkenyl sulfates having from 8 to 24. carbon atoms and of the corresponding alkyl sulfonic acids and of alkyl aromatic sulfonic acids, e. g. the naphthalene aromatic sulfonic acids having an average of 1 to 3 methyl, ethyl, isopropyl, or butyl groups and at least one sulfonic acid group for each naphthalene molecule; the water soluble salts of the condensation products of formaldehyde with naphthalene sulfonic acids, etc. The use of such agents enables color forming development to take place in a more satisfactory manner and inhibits air-bell and bubble formation. They also improve coating uniformity in making such ele- -ments.

-' These elements are not illustrated because their construction can be readily visualized from a study of the existing figures.

The color elements hereof which contain color yielding layers on each-side of a transparent .base may be used for the preparation of multicolor prints as set forth below or in accordance with the processes set forth in the copending application of O. W. Murray, filed December 14, 1940, Serial No. 370,195.

The invention shall be further illustrated but is not intended to be limited by the following examples: a

EXAMPLE I PREPARATION or 3 -Cor.oa Pnmrs A. A cellulose nitrate film base 0.005" thick was coated with a thincellulose glycollateadhesive layer on which was placed a thin cellulose nitrate stripping layer. On the stripping layer was coated a gelatin dispersion containing C. A third color yielding element was made by substituting 1 gram of dibenzoylacetbenzidide per 6.6 g. of gelatin.

They are not synthesized by From three color separation negatives were printed 3 positives on a transparent film base. The positives were bleached in an aqueous solution of potassium ferricyanide to silverierrocyanide images, washed thoroughly, and soaked in 10% NazCOa. The stripping film units A, B and C each were soaked in Diethyl p-phenylenediamine grams 10 misc; do 2 Metol i do 6 11:0 to cc 1000 When these films are saturated with their respective solutions each is squeezed in intimate contact with the proper bleached color separation positives, respectively, until a color image having the layers of elements A and B, A and C,

or B and C on opposite sides of a single transparent base may be similarly processed and a second single color element used therewith.

nxamm -n A. A cellulose acetate film base is coated to form a thin water-soluble adhesive layer from a gelatine dispersion containing about 2 parts of gelatin, 2 parts of dextrin and 96 parts of water. On this layer was superposed a thin membrane or stripping layer composed of collcdion. On the stripping layer is coated a color yielding layer from a gelatin dispersion containing as a bluegreen color former about 1 gram of Z-hydroxy- 3-methyl benzaldehyde phthaldehydic acetal of polyvinyl alcohol per 4 grams of gelatin.

B. A second color yielding unit .was prepared by substituting 4.5 parts of l-(m-octadecoylaminophenyl)-3-methyl-5-pyrazolone for the color former of unit A. I

C. A third color yielding unit was prepared by. substituting 3 parts of acetoacetaminopheynlmorpholine for the color former of unit A.

Three color separation negatives of the type used for 3-color photography were used and processed to form three corresponding positives on a film base. The positive silver images .were then bleached to silver chloride images in a bath of the following composition:

CuSO4 gra'ms 100 NaCl do 100 H2804 conc cc 25 Water to liters 1 Each of the stripping units was soaked in a solution of the following composition:

p-Amino-N-diethylaniline grams 2 Sodium sulfite, anhy do 1 Potassium bromide do. 1 Water to liters 1 form a three color print.

EXAMPLE :1:

Film elements similar to A, B and c of Eb ample I were prepared by substituting for the respective color formers thereof n-octadecylonphenol, 4,4'-bis-(3"-methylpyrazolonyl-l") biphenyloxide, and diacetoacettolidine sulione.

From three color separation negatives were printed three positives on a positive film 'stock. The' positives after development fixing and washing were bleached in a bath of the following approximate composition:

Potassium terricyanide grams 30 Ammonium hydroxide (cone) cc 5 Water to do 1000 washed, and soaked in 10% NazCOa. The respective bleached negatives were then placed in contact and squeegeed with the appropriate color yielding elements A, B and C which hadbeen previously soaked in an energetic developing solution of the following approximate composition:

p-Amino-N-diethylaniline grams 2 Ammonium hydroxide con cc 25 Sodium sulfite, anhy grams 2 Water to liters-.. 1

After the dye images were formed in the color yielding element, the elements were separated, stripped and mounted in register on a white paper base thus forming an excellent -3-color print.

EXAIWPLEIV ,B. A similar element was made by substituting v sodium stearoyl-J-acid for the blue-green dye intermediate of element A.

l .C. A similar element was made by substituting 1-phenyl-3-methyl-4 paradimethylaminobenzol- E-pyrazolone for the dye intermediate 0! element A.

Three bleached positive color component im age records for 3-color photography are made after the maner set forth in Example I and soaked 'with a dilute 5% solution of NaOH and pressed into contact with the respective color yielding layers of elements A and C which is previously soaked in an aqueous solution of the following formula:

\ Parts Monophenylhydrazine 2 2% aqueous sodium oleate 5 Sodium carbon at;- 2

layer are each stripped from the temporary supports and transferred to a permanent paper support to form a three-color print.

EXAMPLE v Film elements similar to'A, B and c of. Example I are made by incorporating in the gelatin dispersions in addition to the dye intermediate about 2 parts of p-amino-N-diethyl-aniline.

,Three bleached positive color separation negatives are made in the manner set forth in ExampleI and soaked in an aqueous bath containing 2% of sodium oleyl sulphate, placed in. pressure contactwith the respective elements A, B

and C, which were previously soaked in an aqueous bath containing 30 cc. of hexamethalene-di amine-1,6 perliter of solution and squeegeed until colored images appear in the outer layers of the color yielding elements.

EXAMPLE VI To a viscose dope consisting of water, cellulose xanthate and caustic soda was added a dilute caustic soda solution of p-hydroxybenzbic' acid positives on themetallic film base were then formaldehyde resin. The resulting solution was flowed on glass plates, coagulated with ammonium sulfate and sodium sulfate-sulfuric acid solutions and cleared with hot dilute sodium carbonate solution. The films were then softened by treatment with glycerol solutions and dried under tension. The resulting element when substituted for element A of Example I gave similar results yielding a goodblue-green dye image. in

a regenerated cellulose film element.

EXAMPLE VII Four strippable dye-yielding elements were prepared as follcws:

(A) Double-weight photographic paper stock was coated with a thin water-soluble adhesive layer from a gelatine dispersion containing about 2 parts of gelatine, 2 parts of dextrine and 96 parts of water. On this layer was coated a thin stripping membrane composed of collodion. On the collodion membrane was coated a coloryielding layer from a gelatine dispersion containing, as a blue-green color former, about 1 gram of 2'-hydroxy-3 -methyl benzaldehyde phthalaldehydic acetal of polyvinyl alcohol per 4 grams of gelatine.

(B) The second color yielding element was prepared by substituting 5.0 parts of 1-.(m-octadecoyl-aminophenyl) -3-methyl-5-pyrazolone for the color former of unit A.

(C) The third color yielding unit was prepared by substituting 2 parts of diacetoacet-tolidine sulfone-o-benzaldehyde sulfonic acid dimer for the color former of unit A.

- 407,830. A fourth positive was printed by combining the red and blue negatives in register and with 10% soaked in a 10% sodium carbonate solution. All

'of the dye-yielding stripping elements A, B, C,

and D were soaked in.a diethyl-p-phenylenediamine color developer as described in Example I. The positives from the individual color separation negatives were rolled into intimate contact with the proper bleached color separation positives until a color image was. formed in. the outer layers of each of such elements. More specifically, the blue-green dye-yielding element was squeegeed into contact with the bleached positive from the red separation negative; magenta yielding element was contact-developed with the positive from ,the green separation negative et cetera. The positive from the combined red and blue negative was contact-developed with the dye-yielding element containing the neutral-gray dye-forming combination. When the color development was completed, the developed dye-yielding elements were stripped from their supports and transferred over to a permanent white support such as barytes coated double-weight paper stock which was previously coated with a thin gelatine layer. The neutral gray key image was transferred first and the dye images were transferred in register onto the base key image.

In this manner there is formed a four-color positive print with remarkably improved color quality with particularly faithful natural color reproduction. By the use of the metallic film base for the positives, it is possible to produce all four of the dye images without serious distortion as may occur in using positive emulsions coated on supports which are water-sensitive thus causing lateral distortion in the dye images and lack of registration. In place of the specific black color formers set forth in this example, other neutral'color formers may be substituted such as, N dodecyl-l; 2-hydroxy naphthoic acid-2- amino carbazole, meta-dodecoylamino-phenylhydroxynaphthothiazole sulfonic acid mixed of 1- (m-stearoylaminophenyl) -3-' methyl-5-pyrazolone; 4- (a-hydroxynaphthoyl- 4'- (p-nitro-benzoylacetyl) -dichloro-benzidide.

Similar elements can be; made by substituting the following color formers for the resin just mentioned: salicylaldehyde-o-sulfobenzaldehyde printing through these onto a positive emulsion coated on aluminum film base. I All four positive prints were developed, fixed'and washed and then bleached to reducible silver ferrocyanide images as described in Example I. The bleached acetal of polyvinyl alcohol, m-aminophenylmethyl pyrazolone o-sulfobenzaldehyde-formaldehyde resin, and the 1-amino-8-naphthol sulfonic acid-ethylene-maleic anhydride interpolymer which when substituted as in Example I yielded blue-green, magneta and blue-green dye images, respectively.

In place of. the specific color yielding elements set forth in the above examples may be substituted a wide variety ofother elements which contain different dye intermediates and coupling components, dispersing agents, wetting agents, adhesives, supports or base materials and membranes as above-described. The resulting color yielding elementsmay be 'used' with photographic elements containing bleached or reducible silver salt images in a similar manner to produce dye images. Thus, regenerated cellulose films ,containing immobile dye intermediates or elements which are essentially composed of film forming dye intermediates can be soaked in developer. solutions or amine solutions and squeegeed with photographic elements containing bleached silver images in asimilar manner.

A plurality of color yielding units may be squeegee-developedin succession with the same ment should, in addition,

photographic element containing bleached or reducible silver salt images. The element, however, must be bleached between each contact development operation. The photographic ele-- be dipped in alkaline solutions between each contact development to insure a uniformity of final prints. For in- .stance, 8 or good prints can be made from an original negative or positive. The photographic elements can be successively bleached and contact-developed to a point of exhaustion of the eles-ient. I

The invention is not limited to the immobile dye intermediates or color formers set forth in the examples, which are of the immobile type. On the contrary, they are merely illustrative of the operability of the invention, but are not intended to limit its scope in any way. In place of the specific color formers may be substituted a large number of exceedingly diverse dye intermediates or color formers capable of forming indophenol, indoaniline, indamine, azomethine or azo dyes by color coupling development. The types which are to be dispersed in gelatin or other similar colloid binding agents are preferably immobile and may be (1) substantive to the gelatin or binding agent, (2) soluble in aqueous alkaline liquids but fast to diifusion when present in emulsion layers, (3) colloidal in nature so that they cannot be removed by simple extraction from the layer, (4) of high molecular weight so that migration through the cellular structure of the binding agent is prevented, (5) highly insoluble, (6) film forming. Substantivity can be strengthened by agents which have precipitating action, e. g. diphenyl guanidide, diphenylbiguanidide, etc.

The immobile dye intermediates or color formers in general contain two components, (1) a color forming dye coupling component or nucleus and a component group or nucleus which increases the molecular weight so that they become immobile in water permeable colloid lay-, ers, or (2) groups for imparting substantive character (which may be of the same type as used in making dyestuffs substantive to cotton), or (3) groups or structures which make itcolloidal in character.

Suitable dyestufi components for color-forming development and azo coupling processes hereof which fall within one or more of the above types of immobile color formers include:

from polyvinyl alcohol or partially hydrolyzed polyvinyl esters and aromatic aldehydes which contain a phenolic hydroxyl, amino, alkyl-, cy-

cloalkyl-, or aryl-substituted amino group ineluding mixed groups of this type, 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 Dorough I; McQueen application, Serial No. 233,480, filed October 5, 1938.

3. Condensation products of phenols and naphthols or hydroxv aromatic carboxylic or sulfonic acids with difunctional resin forming 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 Mc-' Queen application, Serial No. 261,794, filed March 14, 1939.

4. Condensation products of amine-containing dye intermediates such as aminophenols, aminonaphthols, N-aminoallrylor aminoaryl-aminonaththols, amine containing active methylene compounds such as amino aroylor acetyl-acetanilides, amino-phenylmethylpyrazolones or any of the preceding compounds containing solubilizing groups such as carbonyl or sulfonic, with polycarboxylic acids and their derivatives such as 1. Higher aliphatic and cycloaliphatic derivatives of dye intermediates wherein the aliphatic radical such as an alkyl, alkoxy or long chain carboxylic acid acyl radicals contain a carbon chain of more than 8 carbon atoms and preferably at least 12 carbon atoms, such compounds including active methylene compounds such as aroylor acylacetanilides, phenylmethylpyrazolones, etc., higher aliphatic amides -of phenolic compounds, and alphaand beta-naphthols which preferably contain some solubilizing group such as carboxyl or sulf'onic, which are characterized in that they have a reactive position capable of en-' graphic color developers. The acetals are formed the anhydrides, esters, amides o2: halides. Such polymeric acids include the olefin-maleic anhydride interpolymers, polyacrylic .acids and interpolymers of esters of olefin dicarboxylic acids with vinyl esters, olefins and styrene as described in U. S. Patent 1,945,307.

5. Immobile dye intermediates formed from N-mono and dialkylated or 'aralkylated 1,5- and 1,8-aminonaphthols containing in a side chain a group capable of further condensation such as amino, thio, carboxyl, formyl, etc., by condensing said compounds with a suitable high molecular weight compound such as aliphatic acids or amines with more-than 8 carbon atoms or polymeric materials such as polyvinyl alcohol or polymeric acids or derivatives as listed above in paragraph 4.

Suitable immobile dye intermediates of the above and other types which are useful for color development and azo-coupling processes are disclosed in U. 8. Patents 2,154,918, 2,166,181, 2,178,612, 2,179,228, 2,179,238, 2,179,239, 2,179,244, 2,186,045, 2,186,719, 2,186,734, 2,186,736, 2,186,849, 2,140,540, 2,186,735, 2,133,937, 2,200,924, 2,213,986, etc., and may be substituted for the dye intermediates of the above examples in accordance with the-teachings hereof.

Various types of developing solutions and agents which are capable of forming azcmethine or quinoneimine images may be substituted for those of the specific examples.

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, paminodibutylaniline, etc. Other developing agents which may be used include p-phenylenediamine itself, p-methylaminoaniline, p-ethylaminoaniline, p-aminophenol, N,N diethyl-ophenylenediamine, chloro-p-phenylenediamine, 152,5 toluylenediamine, 2 amino .5 diethyl aminotoluene, p-amino-N-phenylmorpholine, N-

p-aminophenylpiperidine, N-methyl-N-hydroxyethyl-p-phenylenediamine, N-butyl-N-hydroxyethyl-p-phenylenediamine, 2-amino-=5- (N-butyl- N-hydroxyethyD-amino toluene, p-y-dihydroxypropyl-p-phenylenediamine, etc. These aromat made of the hydrochloride, sulfates, acetates, etc.

Further examples of developing agents that can be used in this process are-heterocyclic compounds containing benzene nuclei such as 1,2,3,4-tetrahydro-6-aminoquinoline, 1,2,3,4-tetrahydro-G-amino-quinoxaline, etc (U. S. Patent 2,163,820); o-aminophenols and their substitution products; N-hydroxy-alkyl p-phenylenediamines and di-N-hydroxyalkyl p-phenylenedh amines (U. S. Patent 2,108,243); halogenated paminophenols (British Patent, 467,087); pphenylenediamine derivatives containing solubilizing groups in the positive radical connected to the N atom (U. S. Patent 2,163,166).

The developer solutions may further contain various other components of developer solutions. Thus, they may contain organic nitrogen bases free from negative groups and hydroxyl groups attached to carbon and having an association exponent of 5.0 to 11.5 in an amount varying from about 2.5 to 30 or more grams per liter of solution. Suitable agents of this type include primary, secondary and tertiary alkyl monoand polyamines, having one to eight carbon atoms, heterocyclic amines, e. g. piperdine and its homologues, hydrocarbon substituted ammonium hydroxide, etc. Suitable bases are described in the following solutions which have utility in processing the elements hereof. The

bases, however, may be used in water alone after the manner set forth in Example V.

Water to "liters- 1 Bath-F 2-amino-5-diethylamino-toluene grams 5 Trimethy-l benzyl ammonium hydroxide 00.. 20 Sodium sulfite, anhy grams 5 Water to liters 1 Bath-G 4:4 diaminodiphenylamine; grams 4 Hexamethylenediamine cc 10 Sodium sulfite, anhy grams 2 Water to liters 1 Bath-H 12'4-diaminonaphthalene grams 3 Dimethylcyclohexylamine cc 30 Sodium sulfite, anhy "grams" 3. Water to liters 1 Bath-I 4-diethylamino-l-naphthylamine lgrams 5 B dimethylaminoethylamine cc 20 Sodium sulfite, anhy grams 5 Water to liters 1 Bath-J p Aminodibutylaniline grams 3 Hexamethylenediamine solution in methanol) cc 20 Sodium sulfite, anhy grams 2 Water to liters 1 Bath-K I p Aminodiethylaniline gram.s 3 Trimethyl-benzyl-ammonium h y d r 0 xi d e I cc 25 Sodium sulfite, anhy grams 3 Water to liters 1 chloronaphthyl hydrazines, bromonaphthylhydrazines, p-diphenylhydrazines, p,p'-diphenyldihydrazines, p,p'-ditolyldihydrazines, a l p h a naphthylhydrazines, beta naphthylhydrazines which may be 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, long chain aliphatic sulfonic acid salts as 3 set forth in Kirby application, Serial No. 299,762,

filed October 16, 1939, now United States Patent 2,240,929.

In place of the sodium carbonate solutions may be used potassium carbonate, potassium hydroxide, lithium hydroxide and other aqueous Bath-A p-Amino N diethylaniline grams 2 Ammonium hydroxide, conc cc 25 Sodium sulfite, anhy grams '2 Water to liters 1 Bath-B p Aminodiethylanilina"; grams 2 Hexamethylenediamine (55% in methanol) Sodium sulfite, anhy grams 3 Water to liters 1 Bath-C I p Aminodiethylaniline grams' 3 Ammonium hydroxide,pconc cc 30 Sodium carbonate, anhy "grams" 2' Water to liters v 1 Bath-D p Aminodiethylaniline grams 3 B Dimethylaminoethylamine cc 20 Sodium sulfite, anhy grams 3 'Water to--- L liters 1 Bath-E p Aminodiethylaniline g rams 2 Piperidine cc 25 Sodium sulfite, anhy "grams" 2 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 the developing agent and amount of sulfite present.

In general concentrations of 2 to 15% are practical.

In making the above color yielding elements, the color formers may be made into a paste with alkali and brought into solution with water or alcohol and then mixed with an aqueous dis- For example, the

onto a base having a substratum of the type suitable for anchoring silver halide layers. The amount of dye intermediate may be the same as that used'in prior art silver halide layers which contain immobile dye intermediates. The dye intermediate may constitute from 20 to 100% of the weight of the binding agent, i. e. 1 to 5 parts of dye intermediate per 5 parts of binding agent. 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 aikaline aqueous or alcoholic solutions may be cast in a similar manner.

'A number of different bleaching procedures can be used for the elements'which are used for contact development. Filmsor 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.

For the production of color prints and transparencies from strip or continuous film, e. g. colored cine prints or transparencies the dye images can be prepared in the same general manner as.

previously described. The color yielding element preferably should have the same general dimensions as the photographic element for ease of handling and to promote economy. 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 ha 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 theyare mounted in registration with other color component records, e. g. from color separation negatives. of single color elements thesprockets and perforations insureagainst slipping and the production of fuzzy dye image records.

The color yielding units may be used for making single color'prints of various types from photographic elements containing reducible silver salt images in an outer water permeable layer.

However, even in the case 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 in separate elements containingimages other than silver salt images. For instance, one may employ the reducing action of chromium oxides formed by exposing bichromated gelatin 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 e posed film element is then soaked in alkali and pressed into contact with the color yielding element which has been saturated with a color coupling developing solution. In fact, each of the above described procedures for imbibition or con-- tact development can be used with the elements ontaining other types of developable images.

asaaoac A number of advantages are inherent in the processes and articles of this invention. A major advantage resides in the fact' that a simple and economical process of making colored prints is provided. A further object resides in the fact that the invention eliminates a large number of the treating solutions and processing steps used in prior art processes. A further object resides in the fact that light insensitive coloryielding elements which can be processed to color in the presence of light are provided. A further advantage resides in the fact that the color yielding elements do not contain expensive silver salt layers. I

As many apparently widely different embodiments or this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments herein except as defined by the appended claims.

We claim: I

1. The process which comprises impregnating a photographic element containing an image rec- 0rd in reducible silver salts in an outer layer thereof with an aqueous solution, impregnating a color yielding element containing an immobile dye intermediate containing a component capable of forming a dye taken from the group consisting of quinoneimine and azomethine dyes in an outer layer thereof in a reducing solution containing a color coupling developing agent and pressing said outer layersinto contact until a dye image is formed in the latter element. I

2. The process which comprises impregnating a photographic element containing an image record in reducible silver salts in an outer layer thereof with an alkaline aqueous solution, impregnating a color yielding element containing an immobile dye intermediate in an outer layer 5. A process asset forth in claim 2 wherein said developing agent is an aromatic hydrazine.

6. The process which comprises soaking a photographic element containing an image record in reducible silver'salts in an outer layer thereof, soaking a color yielding element bearing a removable outer layer containing an immobile color former in a stratum thereof in a reducing solution containing a color coupling developing agent and pressing said outer layers into contact until a dye image is formed in the latter element.

'7. A process of making color prints which comprises printing positives from color separation negatives, bleaching said positives, soaking said positives in dilute alkali, soaking color yielding elements containing immobile dye intermediates which form dyes corresponding to the color aspects of the separation negatives, in an outer.

layer thereof in a reducing solution containing a color coupling developing agent and pressing said outer layers into contact until a dye image is formed in the latter element, separating said elements and mounting the elements containing dye images in register.

8. A process of making 3-color prints which comprises printing positives from 3-color separation negatives, bleaching said positives, soaking said positives in dilute alkali; soaking color yielding elements containing immobile dye intermediates which form dyes corresponding to the color aspects of the separation negatives, in an outer layer thereof in a reducing solution containing a color coupling developing agent and pressing said outer layers into contact until a dye image is formed in the latter element, separating said elements and mounting the elements containing dye images in register.

9. The process which comprises impregnating a photographic element containing an image record in reducible silver salts in an outer layer thereof with an aqueous alkaline solution, impregnating a color yielding element containing an immobile color former in an outer layer thereof in an aqueous reducing solution containing an aromatic primary amino color developing agent, and pressing said impregnated layers into contact until a dye image is formed in the latter element.

10. The process which comprises printing color separation negatives on to separate light sensitive silver halide elements, developing and fixing said elements, bleaching the metallic silver images in said elements. impregnating the elements in dilute aqueous alkaline solution, arate color yielding elements containing an immobile color former in a water permeable colloid outer layer thereof which forms a dye complementary in color to the color utilized in forming said negatives in an aqueous solution containing a primary amino color developing agent, pressing the outer layers of the respective photographic elements and color yielding elements into contact until a dye image is formed in the latter elements, and mounting the elements containing dye images in register.

11. The process which comprises impregnating a photographic element containing an image recimpregnating sep- 0rd in reducible silver salts in an outer layer thereof with an aqueous solution, impregnating a separate color yielding element containing a dyestuff intermediate capable of color coupling development in an outer layer thereof with an aqueous solution and pressing the impregnated outer layers of said elements into contact while subjecting them to the action of a color coupling developing agent until a dye image is formed in the color yielding element.

12. The process which ing a photographic element which contains an image record in reducible silver salts in an outer layer thereof with an aqueous solution, impregnating a separate color yielding element containing an immobile dyestufi intermediate capable of color coupling development in an outer layer thereof with-an aqueous solution and pressing the impregnated outer layers of said elements into contact while subjecting them to the action of an aromatic primary amino 'color coupling developing agent until a dye image is formed in the color yielding element.

13. The process which comprises impregnating a photographic element containing an image record in reducible silver salts in an outer layer thereof with an alkaline aqueous solution, impregnating a color yielding element containing an immobile dye intermediate capable of forming a dye taken from the group consisting of quinoneimine and azomethine dyes on color coucomprises impregnatpling development in an outer layer thereof in a reducing solution containing an aromatic primary amino color coupling developing agent and pressing said impregnated outer layers into contact until a dye image is formed in the latterelement.

VIRGIL B. SEASE. OTIS W. MURRAY.

Patent No'. 2,528,051

CERTIFICATE OF CORRECTION.

August 51,. 191+ VIRGIL B. SEASE, ET AL.

It is hereby certified that error appears in the printed s pecification of the above numbered patent requiring correction as follows Page )4, first column, line 14.6, for "acetoacetaminopheynl-f reed-- acetoacetaminophenylline 66, before "images" insert --colorpage 5, first column, line 58, for "yeilding" reed "yieldingpage 6, second colun msline 26, for "n'aththols" reao --naphthols-; page 7, first column, line 55, for "piperdine' and that read --piperidinein the Patent Office.

Signed and sealed this 26th day of October, A. D. .1925.

Henry Van Arsdale (Seal) Acting Commissioner of Patents.

the said Letters Patent should be read with this correction therein that the same may 'conform to the record of the case

Images