US3547640A - Multicolor photographic elements - Google Patents

Description

Uited States Patent 3,547,640 MULTICOLOR PHOTOGRAPHIC ELEMENTS Clark Beckett and Bruce D. Folsom, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Continuation-impart of application Ser. No. 621,760, Mar. 9, 1967. This application Jan. 2, 1968, Ser. No. 694,851

Int. Cl. G03c 1/76 U.S. C]. 9674 19 Claims ABSTRACT OF THE DISCLOSURE Multicolor photographic elements which contain at least one nondiffusing, nonbleachable, nonimage-recording colored material incorporated in a support layer and/or one or more hydrophilic colloid layers to compensate for any image dye deficiencies up to about 0.3 density units in minimum density areas of the color reproduction produced upon color processing have an improved neutral scale.

This application is a continuation-in-part of Beckett and Folsom, U.S. Serial No. 621,760, filed Mar. 9, 1967, now abandoned.

This invention relates to color photography and to improved multicolor photographic elements for color photography.

Multicolor photographic elements are well known in the art of color photography. Usually these materials have three selectively sensitized emulsion layers coated on one side of a single support. For example, the outer most layer is generally blue-sensitive. The next layer is generally green-sensitive and the layer adjacent to the support is generally red-sensitive. Between the blue-sensitive and green-sensitive layers a bleachable yellow-colored filter layer is often used for absorbing blue radiation which may be transmitted through the blue-sensitive layer. The multilayer coatings can also have other interlayers for specialized purposes. Such multilayer materials have been previously described in the prior art such as Mannes et a1. U.S. Patent 2,252,718, issued Aug. 19, 1941. Other arrangements of the sensitive layers are also known. Usually the blue-sensitive layer, the green-sensitized layer and the red-sensitized layer are used to produce the yellow-dye image, the magenta-dye image and the cyan-dye image, respectively. Open-chain, pyrazolone, and phenolic (and naphthoic) couplers are usually used for forming the yellow, magenta and cyan dye images. The couplers are either incorporated in the appropriately sensitized emulsion layer or are incorporated in color developer solutions used in processing the exposed photographic materials.

In other multicolor photographic elements packets of blue-sensitive silver halide gelatin emulsions incorporating yellow-forming coupler, packets of green-sensitized silver halide gelatin emulsions incorporating magenta-forming couplers and packets of red-sensitized silver halide gelatin emulsions incorporating cyan-forming couplers are coated in a common layer on the photographic sup ort. The differently sensitized packets are isolated from each other by hydrophilic colloid which serves as the binder for the layer. Such photographic elements have been described by Carroll and Hanson in U.S. Patent 2,259,243, issued Apr. 8, 1952.

Color materials such as those described above are reversal processed by giving them conventional black-andwhite development followed by a reversal exposure(s) color development, bleaching and fixing The three dye images produced in the photographic materials which contain incorporated color-forming couplers are color developed by a single color development step while the photographic materials which do not contain incorporated color-forming couplers must be given separate color development steps for each of the three dye images. Color materials such as those described that contain incorporated color forming couplers are alternatively developed as color negatives by color developing. The color negative is then printed on another color material that also contains incorporated color-forming couplers and which is color developed to produce a color positive of the original image that is used for projection or other viewing. Where it is desired to preserve the original color negative or where special effects are to be introduced, a color intermediate film is used to make from the color negative an intermediate color positive from which a duplicate color negative is made that is used to make the color positive for viewing. It is understood that the exact details of the color elements depend on whether they are designed for color reversal, color negative, color intermediate or color print reproduction, however, this is well known in the art and need not be discussed further here.

In order to achieve good color reproduction in reversal systems the sensitometric curves (relating image dye density with the light exposure) for each of the three image dyes in the processed color material must have the desired relationship. Ideally the sensitometric curves for the three dye images should be identical. Usually methods used to increase the density in a reversal image result in a percentage increase in density throughout the sensitometric curve. In other words, changes to obtain a small increase in dye density in the minimum density area of the reversal dye image will result in very substantial increases in dye density in the upper parts of the sensitometric curves. Oftentimes the increase in dye density that would be produced in the upper scale in order to compensate for a dye deficiency in the minimum density area of the sensitometric curve would be intolerable. As a result, in color reversal reproduction it is often impossible to compensate for dye deficiency in the minimum density regions of the sensitometric curve and the highlight reproduction of a neutral colored original is not neutral as it should be. Similarly, the color balance of reversal image reproduction of non-neutral high-light areas will be distorted. Distorted color balance in the reproduction of human flesh tones is particularly objectionable.

.In color negative-color positive systems of color photographic reproduction, both color negatives as well as duplicate color negatives are used to expose the color print material. Because of differences between color negatives and duplicate color negatives, changes are required in the rinting conditions when changing from negative to duplicate color negative in making a color positive which make it impractical without color timing equipment to inter splice these two films on the same reel. A color negative film is therefore desired which can be intercut with duplicate color negative film on the same reel and used to print (expose) color positive material without any printing condit-ion changes.

It is therefore an object of our invention to provide a novel means for eliminating a minimum dye density deficiency in color image reproduction Without appreciably distorting the color balance in other positions of the sensitometric curve.

Another object of our invention is to provide a novel multicolor element having an improved neutral scale reproduction especially in the minimum density areas.

Another object of our invention is to provide a novel multicolor film for making color negatives that can be intercut on the same reel with duplicate color negatives for exposing color positive film without the need for changing the exposing conditions according to whether the exposure is being made through the color negatives or duplicate color negatives.

Still other objects will be apparent from a consideration of the following specification and claims. These and still other objects are accomplished according to our invention by incorporating at least one nondifl 'usible, nonbleachable, nonimage-recording, light albsorbing colored material in a support layer and/or one or more hydrophilic colloid layers of a multicolor photographic element, to substantially eliminate any image dye deficiency in minimum density areas of image reproductions so that for each of said image dyes that is deficient in minimum density there is incorporated one of our said colored materials having its maximum light absorption at about the same wavelength as the maximum light absorpt-ion of the said image dye formed upon color processing of the color element which is deficient in dye density in the minimum density areas of the image. By dye deficiency in the minimum density we mean a deficiency of one or more dyes which results in inaccurate or even unacceptable color reproduction in highlight areas of an image (e.g., in color reversals or color positives) or a deficiency of one or more dyes in a color negative (or duplicate color negative) material which would make it necessary to use different printing ,(exposure) conditions for making color positives of the negative and duplicate negatives. Our nonimage-recording colored material is advantageously incorporated in the support layer or one or more hydrophilic colloid layers (light-sensitized or not) of the element through which light passes when the developed color reproduction is viewed or used to expose other color elements such as color positive materials. In elements having a transparent support, the colored material is also advantageously incorporated in the support layer or in a hydrophilic colloid layer on the side of the support away from the images. A deficiency in the yellow minimum density is advantageously corrected by incorporating one of our yellow-colored nonirnage-recording materials in one or more of the colloid layers of the element through which the viewing light must pass, i.e., in the blue-sensitive layer or preferably in a colloid layer (sensitized or not) under it. A deficiency in the magenta minimum density is advantageously corrected by incorporating a magenta-colored nonimage-recording material in the green-sensitized layer or a colloid layer (sensitized or not) under it. A deficiency in the cyan minimum density is advantageously corrected by incorporating a cyan-colored nonimage-recording material in the red-sensitized layer or in a colloid layer under it. The cyan-colored nonimage-recording material is also incorporated in a layer above the red-sensitized layer (e.g., an interlayer, the green-sensitized layer, the blue-sensitive layer, etc.), and the magenta-colored nonimage-recording material is also incorporated in a layer above the green-sensitized layer (e.g., an interlayer, the blue-sensitive layer, etc.), however, in these instances it may be necessary to increase the speed of the red-sensitized layer or the green-sensitized layer to compensate for absorption of red or green exposing light by the incorporated colored material.

:A deficiency in an image dye density of up to about 0.3 is advantageously eliminated by incorporating the appropriate amount of the colored material in our novel elements. In some color products such as in color negative materials it is advantageous to eliminate minimum density deficiencies in one, two or even three dyes up to 0.3 density units for each dye. The amount of the colored material needed will depend upon the particular colored material used and can be determined by methods well known in the art. The finely divided dye or pigment particles are added to the hydrophilic colloid or light-sensitive emulsion prior to coating in the form of a suspension in water or other suitable liquid medium by thoroughly mixing. Wetting agents are advantageously used in preparing the suspensions of dye or pigment in water. Incorporation of the 4 dye or pigment in a hydrophobic support layer is advantageously accomplished by init-imately blending finely divided dye or pigment into the dope coating composition or by adding an organic solvent solution of the dye or pigment to the dope coating composition.

Any nondiffusible, nonbleachable, nonimage-recording colored material which has substantially no efiect on the sensitivity of silver halide emulsion can be used to advantage according to our invention. As was mentioned before, the colored material is preferably selected so that it has a maximum light absorption at about the same wavelength as the maximum light absorption of the image dye that is deficient in the minimum density areas of the developed image. Included among the dyes used to advantage according to our invention are the azomethine dyes formed by the reaction of oxidized color developer and open-chain couplers or 5-pyrazolone couplers; the indoaniline dyes formed by a reaction of oxidized color developer and phenolic or naphthoic couplers; vat dyes such as indigo and its derivatives, thioindigo and its derivatives, and indanthrene yellow GK and its derivatives; azo dyes, etc. Included among pigments used to advantage according to our invention are the phthalocyanines; the benzidine textile colors and diazo-substituted triphenyl methanes.

Yellow-colored azomethine dyes used according to our invention included those shown by the formula:

II N I N R4/ R5 wherein R represents an alkyl group (substituted or not) preferably having from 1 to 32 carbon atoms (e.g., methyl, butyl, tertiary butyl, norbornyl, 1,1-diethyloctyl, benzyl, octadecyl, 1,1 didecyloctadecyl, 1 phenyl-cyclohexyl, etc.); an aryl group (e.g., naphthyl, phenyl, 2-methoxyphenyl, 2 octadecyloxyphenyl, 2-chlorophenyl, 2,4-dibromophenyl, 2,4,6-trichlorophenyl, 4-[et-(4-tert.-amylphenoxy)-butyramido]phenyl, etc.) etc.; R represents hydrogen, an alkyl group having from 1 to 18 carbon atoms (e.g., methyl, butyl, octyl, octadecyl, etc.); an aryl group (e.g., phenyl, tolyl, chlorophenyl, etc.); n is an integer from 1 to 2; R represents hydrogen, an alkyl group having from 1 to 18 carbon atoms (e.g., methyl, decyl, octadecyl); an aryl group (e.g., naphthyl, methoxyphenyl, chlorophenyl, 2,4 dichlorophenyl, 2,4,6-trichlorophenyl, 4 [a (4 tert.-butylphenoxy)butyramidoqphenyl, 2- chloro 5 [oz (2,4 di-tert.-amylphenoxy)acetamido] phenyl, 2 chloro-S-[et-(2,4-di-tert.-amylphenoxy)butyram1do]phenyl, 2-chloro-5-(4-methylphenyl sulfonamido) phenyl, 4 [N ('y-phenylpropyl)-N-(p-tolyl)-carbamylmethoxy]phenyl, etc.); R represents hydrogen, a lower alkyl group, (e.g., methyl, ethyl, [i-methane sulfonamidoethyl, butyl, etc.); R represents hydrogen, lower alkyl (e.g., methyl, ethyl, amyl, B-methane sulfonamidoethyl, etc.); R represents an alkyl group having from 1 to 11 carbon atoms (e.g., methyl, ethyl, fl-methane sulfonamidoethyl, decyl, etc.).

The magenta colored azomethine dyes used advantageously include those represented by the formula:

wherein R, R R and R are as defined previously and R represents the groups defined previously for R and in addition hydrogen, a carboxy ester group (e.g., carbopropoxy, carbobutoxy, carboethoxy, etc.), a substituted oxy group (e.g., methoxy, decyloxy, phenoxy, tolyloxy, etc.), a substituted thio group (e.g., ethylthio, propylthio, toly1- thio, etc.), an amino group (e.g., amino, N-alkylamino, N-arylamino, N,N-dialkylamino, N-alkyl-N-arylamino, etc.), an amido group (e.g., acetamido, u-(2,4-di-t-amylphenoxy)acetamido, a-butylphenoxypropionamido, a-(3- pentadecyl-4-sulfophenoxyacetamido)benzamido, etc.), a carbamyl group (e.g., carbamyl, N-octadecylcarbamyl, N,N-dihexylcarbamyl, N-methyl-N-phenylcarbamyl, 3- pentadecylphenylcarbamyl, etc.), sulfamyl, a ureido group (e.g., an N-arylureido group, an N-alkylureido group, etc.), a thioureido group (e.g., an N-alkylthioureido group, an N-arylthioureido group, etc.), a guanidino group (e.g., guanidino, N-arylguanidino, N-alkylguanidino, etc.).

The cyan indoaniline dyes used to advantage include those represented by the formulas:

III

wherein R R and R are as defined previously; R and R represent any of the groups described previously for R and in addition represents hydrogen, amino (e.g., methylamino, diethylamino, docosylamino, phenylamino, tolylamino, 4 (3-sulfobenzamido) anilino, 4-cyanophenylamino, 2-trifuloromethylphenylamino, benzothiazolamino, etc.), a carbonamido group (e.g., an alkylcarbonamido group, such as ethylcarbonamido, decylcarbonamido, phenylethylcarbonamido, etc.), an arylcarbonamido group (such as, phenylcarbonamido, 2,4,6 trichlorophenylcarbonamido, 4 methylphenylcarbonamido, 2 ethoxyphenylcarbonamido, 3 [a (2,4, di-tertamylphenoxy)acetamido]benzamido, naphthylcarbonamido, etc.), a heterocyclic carbonamido group (such as thiazolylcarbonamido, benzothiazolylcarbonamido, naphthothiazolylcarbonarnido, oxazolylcarbonamido, benzoxazolylcarbonamido, imidazolylcarbonamido, benzimidazolylcarbonamido, etc.), a sulfonamido group (e.g., an alkylsulfonamido group, such as, butylsulfonamido, docosylsulfonamido, phenylethylsulfonamido, etc.), an arylsulfonamido group (such as phenylsulfonamido, 2,4,6-trichlorophenylsulfonamido, 2 methoxyphenylsulfonamido, 3 carboxyphenylsulfonamido, naphthylsulfonamido, etc.), a heterocyclic-sulfonamido group (such as thiazolylsulfonamido, benzothiazolylsulfonamido, imidazolylsulfonamido, benzimidazolylsulfonamido, pyridylsulfonamido, etc.), an alkylsulfamyl group (e.g., propylsulfamyl, octylsulfarnyl, pentadecylsulfanyl, octadecylsulfamyl, etc.), an arylsulfamyl, (such as, phenylsulfamyl, 2,4,6-trichlorophenylsulfamyl, Z-methoxyphenylsulfamyl, naphthylsulfarnyl, etc.), a heterocyclic sulfamyl group (such as a thiazolylsulfamyl, a benzothiazolylsulfamyl, an oxazolylsulfamyl, a benzimidazolylsulfamyl, a pyridysulfamyl group, etc.), an akylcarbamyl (such as ethylcarbamyl, octylcarbamyl, pentadecylcarbamyl, octadecylcarbamyl, etc.), an arylcarbamyl, such as phenylcarbamyl, 2,4,6 trichlorophenylcarbamyl, etc., a heterocyclic carbamyl group (such as a thiazolylcarbamyl, a benzothiazolylcarbamyl, an oxazolylcarbamyl, and imidazolylcarbamyl, benzimidazolylcarbamyl group, etc.).

t 6 Our invention is still further illustrated by the following typical colored materials that are used to advantage in our novel photographic elements.

( 1 2,2-disulfo-4,4'-bis (p-propyloxyphenylazo) stilbene (2) 4,4-bis a- (phenylcarbamyl) -m- (acetyl methylazo] 3,3'-dichlorobiphenyl (3) 4,4-bis a- (o-tolylcarbamyl) -uacetyl methylazo] 3,3 '-dichlorobiphenyl (4) Ot-PiVa1yl-OL- [4- (N-ethyl-N-,B-methanesulfonamidoethyl) aminophenylimino] -acetanilide 5) a{ 3 (2,4-ditert.-arnylphen0xy butyramido] benzoyl}-a- [4- (N,N-diethylaminophenylimino] -2-methoxy-acetanilide (6) a-(Z-ethOXy) benzoyl-a-[4-(N-ethy1-N-B-methanesulfonamidoethyl) aminophenylimino] -3- ['y- (2,4-ditert.-amylphenoxy) butyramino acetanilide (7) Indanthrene yellow GK (8) Indigo (9) Phthalocyanine blue (Color Index 74160) (10) 2- [6- (2,4-di-tert.-amylphenoxy)butylcarbamyl) -1,4- p-N,N-diethylaminophenyl) ]naphthoquinone mono- 1m1ne (11) 2-{4- [a- (4-tert.-amylphenoxy) -n-butylamino] benzoylamino}-1,4- [p-(N,N-diethylaminophenyl) qumone monoimine (12) Thioindigo 13 2,2,5 ,5 -tetramethyltriphenylmethane-4,4'-bis(azo- Z-N-heptoyl H acid) 14) 1- (2,4,6-trichlorophenyl -3-{3- [a-ZA-di-tertamylphenoxy acetamido] benzamido}-4- (4-N,N-diethy1- aminophenylimino -5 -pyrazo1one 15 1- 2,4,6-trichlorophenyl) -3- (4-nitroanilino -4-(4- N-ethyl-N-B-methanesulfonamidoethyl aminophenylimino] -5-pyrazolone (16) 1- (2,6-dichloro-4-cyanophenyl) -3- 2,4-dichloroanilino -4- (4-N,N-diethylaminophenylimino) -5pyrazolone (17) 1- (2,4-dichloro-4-nitrophen'yl) -3- 2,4-dichloroanilino -4- (4-N,N-diethylaminophenylimino 5- pyrazolone While the examples used herein are concerned primarily with silverbrornoiodide, it is understood that the silver halide emulsions can be employed such as silver chloride, chloroiodide, chlorobromoiodide, and bromoiodide developing-out emulsions. These emulsions can be coated in the usual manner on any support, such as glass, cellulose nitrate film, cellulose acetate film, polyvinylacetyl resin film, paper, etc.

The emulsions can be chemically sensitized by any of the accepted procedures. The emulsions can be digested with naturally active gelatin, or sulfur compounds can be added such as those described in Sheppard US. Pat. 1,574,944, issued Mar. 2, 1926, Sheppard et al. US. Pat. 1,623,499, issued Apr. 5, 1927, and Sheppard et al. US. Pat. 2,410,689, issued Nov. 5, 1946.

The emulsions can also be treated with salts of the noble metals such as ruthenium, rhodium palladium iridium, and platinum. Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropaladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli US. Pat. 2,448,060, issued Aug. 31, 1948, and as antifoggants in higher amounts, as described in Trievelli and Smith U.S. Pats. 2,566,245, issued Aug. 28, 1951, and 2,566,263, issued Aug. 28, 1951.

The emulsions can also be chemically sensitized With gold salts as described in Waller et al. US. Pat 2,399,083, issued Apr. 23, 1946, or stabilized with gold salts as described in Damschroder US. Pat. 2,597,856, issued May 27, 1952, and Yutzy and Leermakers US. Pat. 2,597,- 915, issued May 27, 1952. Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium 7 chloroaurate, auric trichloride and 2-aurosulf0benzothiazole methochloride.

The emulsions can also be chemically sensitized with reducing agents such as stannous salts (Carroll US Pat. 2,487,850, issued Nov. 15, 1949), polyamines, such as, diethyl triamine (Lowe and Jones US. Pat. 2,518,698, issued Aug. 15, 1950), polyamines, such as spermine (Lowe and Allen US. Pat. 2,521,925, issued Sept. 12, 1950), or bis(fi-aminoethyl)sulfide and its water-soluble salts (Lowe and Jones US. Pat. 2,521,926, issued Sept. 12, 1950).

The emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Pats. 1,846,301, issued Feb. 23, 1932; 1,846,302, issued Feb. 23, 1932; and 1,942,854, issued Jan. 9, 1934; White US. Pat. 1,990,507, issued Feb. 12, 1935; Brooker and White U.S. Pats. 2,112,140, issued Mar. 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued Jan. 10, 1950, and 2,739,964, issued Mar. 27, 1956; Brooker and Keyes US. Pat. 2,493,748, issued Jan. 10, 1950; Sprague U.S. Pats. 2,503,776, issued Apr. 11, 1950, and 2,519,001, issued Aug. 15, 1950; Heseltine and Brooker US. Pat. 2,666,761, issued Jan. 19, 1954; Heseltine U.S. Pat. 2,734,900, issued Feb. 14, 1956; Van Lare U.S. Pat. 2,739,149, issued Mar. 20, 1956; and Kodak Limited British Pat. 450,958, accepted July 15, 1936.

In the preparation of the silver halide dispersions employed for preparing silver halide emulsions, there may be employed as the dispersing agent for the silver halide in its preparation, gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound. Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe US. Patent 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 1926% as described in US. Patent 2,327,808 of Lowe and Clark, issued Aug. 24, 1943; a water-soluble ethatnolamine cellulose acetate as described in Yutzy U. S. Patent 2,322,085, issued June 15, 1943; a polyacrylamide having a combined acrylamido content of 30-60% and a specific viscosity of 0.25-1.5 on an imidized polyacrylamide of like acrylamide content and viscosity as described in Lowe, Minsk and Kenyon US. Patent 2,541,474, issued Feb. 13, 1951; zein as described in Lowe US. Patent 2,563,791, issued Aug. 7, 1951; a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in Unruh and Smith US. Patent 2,768,154, issued Oct. 23, 1956; or containing cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest US. Patent 2,808,331, issued Oct. 1, 19-56; or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in US. Patent 2,852,382, of Illingsworth, Dann and Gates, issued Sept. 16, 1958.

If desired, compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide in its preparation. Combinations of these antifoggants, sensitizers, hardeners, etc., may be used.

The light-sensitive silver halide hydrophilic colloid emulsion used in our elements advantageously contain any of the stabilizers, speed-increasing compounds, gelatin plasticizers, hardening agents, coating aids and other addenda such as are used in color photographic elements and described in Yager et al. US. Patent 3,113,864, particularly in columns 10, 11 and 12.

In our photographic elements which contain incorporated couplers, any of the nondiffusing color forming couplers commonly used in color photography are used to advantage. These couplers include those described by US. Patents 2,956,876 (column 5, lines 30-59), 2,407,- 210, 2,423,730, 2,474,293, 2,600,788, 2,640,776, 2,875,- 057, etc.

Any of the well-known diffusible couplers used in the color developer solutions are used to color develop our photographic elements that do not contain incorporated couplers. These couplers include those described by US. Patents 2,266,452, 2,295,009, 2,313,586, 2,362,598, 2,369,- 929, 2,772,162, 3,002,836, 2,311,082, 2,353,205, 2,369; 489, 2,600,788, 2,343,703, 2,899,306, 2,115,394, 2,108,- 602, 2,113,330, 2,271,238, 2,289,805, 2,439,352, etc.

Any of the well-known primary aromatic amino silver halide developing agents, such as the p-phenylenediamines including the alkyl phenylenediamines and the alkyl toluenediamines, and the primary p-aminophenols are used to advantage in the color development of our elements.

The colored materials used in our elements are unbleachable. By unbleachable we mean that they are not decolorized by the processing solutions used in color processmg.

The following examples will still further illustrate our invention.

EXAMPLE 1 A multilayer color film (Coating 1) is prepared as described in FIG. 2 of Mannes et al. US. Patent 2,252,- 718, issued Aug. 19, 1941. This film has a support coated in succession with a silver bromoiodide gelatin emulsion red-sensitized to a peak at about 590 Ill/L with a thiacarbocyanine dye, a gelatin interlayer, a silver bromoiodide gelatin emulsion green-sensitized to a peak at about 500 with a 2,2-cyanine sensitizing dye combined with a thia- 2-cyanine dye, a gelatin interlayer containing a bleachable yellow-colored dye, and a blue-sensitive silver bromoiodide gelatin emulsion. The above dyes are of the type shown by Mees in Second Printing 1959 of The Theory of the Photographic Process on pages 379 through 381. A second color film (Coating 2) is prepared the same as Coating 1 except that hthalocyanine blue (Color Index 74160) is added to the red-sensitized silver bromoiodide gelatin emulsion prior to coating so that 3 milligrams of the pigment is coated per sq. ft. This pigment, coated at this coverage, yields a density of about 0.05 density units to light at 650 mg. The pigment is added to the emulsion in the form of a suspension in water prepared by thoroughly mixing the following ingredients.

Grams Phthalocyanine 10 4-(1,1,3,3 tetramethylbutyl) phenoxyethoxyethylsulfonate sodium salt Water 52 TABLE 1 Minimum dye density Coating No. Pigment Yellow Magenta Cyan 1 Absent 16 16 l0 2 Present- .15 15 14 It an be seen from the above results that the D-min. of the cyan dye image in Coating 1 is less than the minimum densities of the yellow and magenta dye images. Consequently, the highlight areas of the processed coating appear pink. In Coating 2 which contains the cyan pigment, however, the minimum densities of the cyan, magenta, yellow dye images are substantially equal so that the highlight areas of the processed coating appear neutral in tone. A comparison made of the sensitometric curves show that while the incorporation of the pigment makes the minimum density of the cyan dye curve for coating 2 equal to the magenta and yellow minimum 9 densities, the presence of the pigment does not distort the color balance throughout the rest of the sensitometric curve (tonal scale).

The exposed Coatings 1 and 2 of Example 1 are processed through the following steps:

Step: Time Prehardener 2 min. Water wash 30 sec. MQ developer 3 min., 40 sec. Water wash l min. Red light exposed through support Cyan developer 4min., 30 sec. Water Wash 2 min. Blue light exposed through emulsion Yellow developer 4 min. Water wash 2 min. Borohydride bath 1 min. Water wash 30 sec. Magenta developer 5 min., sec. Water wash 4 min. Ferricyanide bleach 2 min. Hypo fix bath 2 min. Water wash 4 min. Dry.

The solutions have the compositions given below:

Prehardener:

Sodium hexametaphosphate0.5 g. Sulfuric acid1.7 ml. Sodium tetraborate-5H O15.0 g. Sodium bromide2.0 g. Sodium sulfate200.0 g. Formalin (37.5% )20.0 ml. Sodium bisulfite1.0 g. Water to make 1 liter. MQ developer:

Sodium hexametaphosphate0.6 g. Sodium sulfite79.0 g. Monomethyl-p-aminophenyl sulfate-5 .0 g. Sodium hydroxide1.0 g. Hydroquinone-2.0 g. Sodium carbonate- .0 g. Potassium iodide (0.1% )12.5 ml. Sodium bromide-3.0 g. Sodium thiocyanate-1.7 g. Hydroquinone monosulfate4.0 g. Water to make 1 liter. Cyan developer:

Sodium hexametaphosphate0.6 g. Sodium bromide2.5 g. S-nitrobenzimidazole nitrate (1% in .l% NaOH)- 3.0 ml. Potassium iodide (0.1% )11.0 ml. Sodium sulfite10.0 g. Sodium sulfate-60.0 g. Sodium hydroxide3.8 g. Sodium thiocyanate-1.0 g. Hydroxylamine sulfate0.65 g. 4-amino-N-ethyl-N-fi-hydroxyethyl-3-methylaniline sulfate2.05 g. l-hydroxy-N- 2-acetamidophenethyl) -2- naphthamide1.65 g. Hexylene glycol-5 .0 ml. Polyoxyethylene (M. wt. 1540)1.0 g. N-benZyl-p-aminophenyl.45 g. Methanol2.0 ml. p-Aminophenol-.l6 g. Water to make 1 liter. Yellow developer:

Sodium hexametaphosphate0.6 g. Sodium sulfite-10.0 g. Sodium bromide.55 g. Polyoxyethylene (M. Wt. 4000)1.0 g. Potassium iodide (0.1% )26 .0 m1. N,N-diethyl-p-phenylenediamine HCl-3 .0 g.

10 5-nitrobenzimidazole10.0 ml. Sodium hydroxide2.1 g.

Sodium sulfate-64.0 g. Hexylene glycol10.0 ml. ot-Benzoyl-2-methoxyacetanilide1.5 g. Diethylhydroxylamine-l.38 ml. 1-phenyl-3-pyrazolidone0.5 g. Water to make 1 liter.

Borohydride bath:

Sodium hexametaphosphate0.6 g. Sodium hydroxide-2.16 g. Potassium borohydride0.1 i) g. Water to make 1 liter Magenta developer:

Sodium hexametaphosphate4.0 g. Sulfuric acid-2.1 ml. Sodium phosphate l2H O40.0 g. Sodium sulfite5.0 g. Sodium thiocyanate1.0 g. Potassium iodide (0.1% )7.5 ml. Sodium bromide-0.5 g. Sodium sulfate-60.0 g. 4-amino-N-ethyl-N- (fi-methanesulfonamidoethyl m-toluidine sesquisulfate monohydrate2.9 g. Citrazinic acid0.72 g. Ethylenediamine3 .0 ml. Polyoxyethylene (M. wt. 4000)1.0 g. Hexylene glycol-l0.0 ml. 1-(2,4,6-trichlorophenyl)-3-(4-nitroanilino)- 5-pyazolone-1.67 g.

Sodium hydroxide-0.32 g. Water to make 1 liter.

Ferricyanide bleach bath:

Sodium bromide35 .0 g. Potassium ferricyanide'1OH -200.0 g. Sodium hydroxide--0.1 g. Sodium tetraborate-5H Ol.0 g. Water to make 1 liter.

Hypo fix bath:

Sodium thiosulfate220.0 g. Sodium sulfite10.0 g. Sodium hydroxide-15 g. Water to make-1 liter.

Similar results are obtained by using other cyan-colored material, including illustrative colored materials 8 through 11, and the dyes of Formulas III :and IV, in the red-sensitized silver halide gelatin emulsion layer, a hydrophilic colloid layer under the red-sensitized layer or in the transparent support layer of our photographic materials. In less preferred embodiments of our invention, phthalocyanine blue and other cyan-colored materials are also used advantageously incorporated in either the green-sensitized silver halide emulsion layer or in the blue-sensitive silver halide emulsion layer. When the cyan-colored material is incorporated in one of the layers above the red-sensitized silver halide emulsion layer a small amount of the red-light exposure will be absorbed by the cyan-colored material so that it may be necessary to increase the red-sensitivity of the red-sensitized layer accordingly.

ln multicolor, multilayer photographic elements in which the minimum density of the developed image has a deficiency in yellow dye, it is advantageous to incorporate one of the yellow-colored nondiffusible, nonremovable and nonimage-recording materials of our invention. The appropriate amount of the yellow-colored material is advantageousiy incorporated in any of the light-sensitive layers, hydrophilic colloid interlayers or in the transparent support layer of our photographic element. The following example will illustrate the incorporation of a yellowcolored material in the blue-sensitive silver halide emulsion layer of a multicolor element.

EXAMPLE 2 A multilayer color film Coating 3 (control) is made similar to that described in Example 1, however, this film 1 1 upon exposure and processing as described in Example 1 gives a color reproduction in which the yellow dye image in the minimum density is 0.02 density units less than the identical D-mins. of the cyan and magenta dyes. A multilayer color film Coating 4 is made just like Coating 3 excepting that a dispersion of the yellow dye bis-[2,2'-disulfo-4,4'-(p,p'-dipropyloxyphenylazo) ]stilbene in water is incorporated in the blue-sensitive silver bromoiodide gelatin emulsion before it is coated. Sufficient yellow dye is incorporated so that the blue-sensitive layer contains one milligram of the dye per square foot of coating. When Coating 4 is exposed and processed as described in Example 1, the yellow, cyan and magenta D-min. values are the same. The incorporation of our nondiifusible, nonbleachable, nonimage recording yellow dye in Coating 4 eliminates the yellow dye deficiency in the D-min. and produces no apparent change in the color balance of the rest of the tonal scale.

EXAMPLE 3 A multilayer color film Coating 5 (control) is made similar to that described in Example 1, however, this film upon exposure and processing as described in Example 1 given a color reproduction in which the cyan and magenta D-mins. are identical and the yellow D-min. is a 0.03 density unit lower. A multilayer color film Coating 6 is made like Coating 5 except that a dispersion of the yellow pigment 4,4-bis oc- (phenylcarbamyl -aacetyl methylazo 3,3'-chlorobiphenyl is incorporated in the blue-sensitive silver bromoiodide gelatin emulsion so that 3 milligrams of the pigment are coated per square foot. The coatings are sensitometrically exposed and processed as described in Example 1. The yellow D-min. in our Coating 6 is identical to the cyan and magenta D-mins. A comparison of processed Coatings 5 and 6 shows that there is no appreciable shift in the color balance in the middle tones and D-max. produced by the addition of yellow pigment in Coating 6.

EXAMPLE 4 Another multilayer color film Coating 7 (control) is made similar to that described in Example 1 but which upon exposure and color processing as described in Example 1 has a yellow D-min. that is 0.04 density units below the cyan and magenta D-mins. Coating 8 is identical to Coating 7 excepting that there is incorporated enough of the yellow pigment used in Example 3 to coat 5 milligrams of the pigment per square foot. Upon exposure and processing as described in Example 1, our Coating 8 has identical yellow, cyan and magenta D-mins. while the control yellow D-min. is a 0.04 density unit too loW.

Similarly it can be shown that any of the other yellowcolored nondifiusing, nonbleachable and nonimage-recording materials of our invention can be used according to our invention including the colored materials 1 through 7 and other dyes described by Formula I.

EXAMPLE 5 A multilayer color film Coating 9 (control) is made similar to that described in Example 1 but which upon exposure and color processing produces an image with identical cyan and yellow D-mins. but a magenta D-min. that is 0.03 lower. A multilayer color film Coating 10 is made identical to Coating 9 but has enough of a dispersion in Water of the magenta-colored material 2,2,5,5-tetramethyltriphenylmethane-4,4'-bis(azo-2-N-heptoyl H acid) so that the coating contains 0.9 milligram of the colored material per square foot. A comparison of exposed and processed samples of Coatings 9 and 10 show that although the incorporation of the magenta-colored material produces no apparent change in the color balance of the middle tone and D-max., the 0.03 desity unit deficiency in magenta D-min. in control Coating 9 is eliminated in Coating 10.

In those cases Where it is desired to use a magentacolored dye or pigment according to our invention this can be advantageously incorporated in the red-sensitized silver halide emulsion, in the transparent support layer, in a hydrophilic colloid interlayer or in the blue-sensitive emulsion as well as in the green-sensitized emulsion illustrated in Example 5. The incorporation of a magentacolored material in the top blue-sensitive layer or hydrophilic colloid layer between the blue-sensitive and green sensitive layers will produce a slight decrease in the exposure of the green-sensitized layer and it may be necessary to increase the speed of this layer to compensate for this.

Similarly, it can be shown that still other magentacolored materials can be used according to our invention including colored materials 12 through 17 and other dyes of Formula II.

Although it is possible to distribute the colored material in two or even three of the hydrophilic colloid layers, it is generally preferable to confine this to a single layer.

Usually our colored materials are incorporated to correct for minimum density deficiencies in image dye in the range up to about 0.3 density units and usually in the range from about 0.02 to about 0.3 density units. The concentration at which a particular colored material is coated to produce the desired density increase will depend upon the particular colored material being used. The optimum concentration can be obtained by making a series of coatings which differ in the concentration of the colored material. We have found, for example, that the colored materials used in Example 2 and in Example 5 are used most advantageously in the concentration range from about 0.5 to about 2.0 milligrams per sq. ft. of coating. The concentration of the dye used in Example 3 is most advantageously used in the range from about 1 to about 5 milligrams per sq. ft.

Multicolor photographic elements in which the differently sensitized silver halide grains are coated in a single emulsion layer as described by Carroll et al. in U.S. Patent 2,592,243 sometimes have a deficiency in the minimum density of one of the developed colored images. Such a deficiency is advantageously corrected by incorporating the required amount of the appropriately colored nondisffusible nonremoveable, nonimage-recording colored material according to our invention in the lightsensitive layer.

Although the examples shown above illustrate photographic elements which have a deficiency of only one image dye in the minimum density areas of the color reproduction, some photographic elements have a deficiency in two or even three dye images (in the minimum density). In these photographic elements the appropriate amounts of the dyes or pigments of the appropriate color are used to advantage according to our invention to substantially eliminate the deficiencies in these dye densities.

The following examples will illustrate another embodiment of our invention in which three differently colored materials are used to eliminate deficiencies in minimum densities of three image dyes in a color negative material so that color negatives made on it can be intercut with duplicate color negatives on a reel and these used to expose color positive material without making changes in the exposure conditions normally required when changing from color negative to duplicate color negative and vice versa.

EXAMPLE 6 A color negative film identified as A is made by coating on a transparent film support in succession a red-sensitized silver bromoiodide emulsion containing a nondiffusing cyan-forming coupler, such as those described in 0 U.S. Patent 2,423,730, a green-sensitized silver bromoiodide emulsion containing a nondiffusing magenta-forming S-pyrazolone coupler, such as those described in U.S. Patent 2,600,788, a blue-sensitive silver bromoiodide emulsion containing a nondiffusing yellow-forming benzoylacetoalkoxyanilide coupler, such as those described in US. Patent 2,875,057, and a gelatin overcoat. A color negative film identified as B is made identically to A except that a sufiicient amount of phthalocyanine blue pigment suspended in water containing 4-(1,1,3,3-tetramethylbutyl)phenoxyethoxyethylsulfonate sodium salt (as described in Example 1) is incorporated in the red-sensitive emulsion prior to coating to produce in the coated element an increase of about 0.3 density units to red light, a suflicient amount of a dispersion in water of 2,2',5,5'- tetramethyltriphenylmethane-4,4'-bis-(azo-2-N-heptoyl H Acid) is incorporated in the green-sensitized emulsion prior to coating to produce in the coated element an increase of about 0.2 density units to green light, and a sufficient amount of a dispersion in water of 4,4-bis-[ot- (phenylcarbamyl)-a-(acetyl)methylazo] 3,3'-dichlorobiphenyl is incorporated in the blue-sensitive emulsion prior to coating to produce in the coated element an increase of about 0.1 density unts to blue light. Pieces of the color negative films A and B are exposed to an original light image and given color negative processing as is described in detail by W. T. Hanson, Jr., and W. I. Kisner in the Journal of the SMPTE (i.e., the Society of Motion Picture and Television Engineers), 61, pages 667-701 (1953) to produce color negatives A and B, respectively. The processed D-min. values for the color negatives are given below.

D-min. of D-min. of color negative A color negative B .93 to blue light 1.03 to blue light. .57 to green light .77 to green light. .10 to red light .40 to red light.

Color intermediate film is exposed to light through color negative A and the exposed color intermediate film is processed to produce intermediate color positive A. Another piece of color intermediate film is exposed to light through intermediate positive A and the exposed film processed to produce duplicate color negative A. The same procedure is used to produce duplicate color negative B derived from color negative B. Color intermediate film and processing are described by Hello, Groet, Hanson, Osborne and Zwick in A New Color Intermediate Positive-Intermediate Negative Film System for Color Motion Picture Photography, Journal of the SMPTE, 66, pages 205-209 (April 1957). Additional information on the details of processing color negatives and color intermediate films is given in Abridged Specifications for Deep-Tank Processing of Eastman Color Films dated May 1967, published by Motion Picture and Education Markets Division, Eastman Kodak Company, Rochester, New York, 14650. When the processed color negative film A (prior art) is interspliced with a piece of a duplicate color negative A (or B) and used to expose a piece of color positive film with exposure conditions balanced for the duplicate color negative and color positive film, the processed color positive made from the duplicate color negative is a good reproduction of the original light image while the processed color positive reproduction of the original light image made directly from the color negative is unacceptable. The exposed color positive film is processed in the process described in detail in the Hanson and Kisner reference cited above. Similarly, when the exposure conditions are balanced for the color nega-' tive and color positive films, good color positive reproductions of the original light image are obtained from the color negative but unusuable reproductions of the original light are obtained from the duplicate color negative. Attempts to find a compromise exposure condition give unacceptable results. When the color negative B of our invention is interspliced with the duplicate color negative A (or B) and used to expose another piece of the color positive film used above with exposure conditions balanced for the duplicate color negative film and color positive film, good reproduction of the original light 14.- image is obtained from both our color negative B and duplicate color negative A (or B).

EXAMPLE 7 A color negative film identified as C (prior art) is made like color negative film A but with gelatin interlayers between each of the light-sensitive layers and between the red-sensitized layer and the suport layer. A color negative film identified as D (of our invention) is made like C but a suflicient amount of phthalocyanine blue pigment suspended in water containing 4-(l,1,3,3-tetramethylbutyl) phenoxyethoxyethylsulfonate sodium salt is incorporated in the gelatin layer between the red-sensitized layer and the support layer to produce an increase of about 0.3 density units to red light, a sufficient amount of a dispersion in water of 2,2,5,5-tetrarnethyltriphenylmethane- 4,4-bis-(azo-2-N-heptoyl H Acid) is incorporated in the gelatin layer between the red-sensitized layer and the green-sensitized layer to produce in the coated element an increase of about 0.2 density units to green light and a sufiicient amount of a dispersion in water of 4,4'-bis-[m- (phenylcarbamyD-ot-(acetyD-methylazo] 3,3 dichlorobiphenyl is incorporated in the gelatin layer between the green-sensitized layer and the blue-sensitive layer to produce in the coated element an increase of about 0.1 density units to blue light. Pieces of the color negative C and D are exposed and processed as described in Example 6 to make color negatives C and D. Using color intermediate film duplicate color positives C and D and duplicate color negatives C and D are made from color negatives C and D, respectively, by a procedure like that described in Example 6. Pieces of color negatives C and D are interspliced on a roll with pieces of duplicate color negatives C and D. Color positive film is exposed through the roll of interspliced color negatives and duplicate color negatives using exposing conditions balanced for the duplicate color negative and the color positive materials. When processed, the color positives made from color negative D and duplicate color negatives C and D are good reproductions of the original light image but the color positive made from color negative C is an unacceptable reproduction of the original light image. Variations in exposure conditions are made but no single exposure condition is found which will produce acceptable color positives from both color negative C and duplicate color negative C (or D).

Similarly the other colored materials of our invention are used to advantage as described in Examples 6 and 7 in place of the colored materials used therein. It is to be understood that the amounts of the colored materials needed in the color negative material according to our invention will depend upon a number of factors including the specifications of the color negative material, the color intermediate material and the respective processes. For certain color negative products only one or two colored materials are needed instead of the three illustrated in Examples 6 and 7. While the illustrative examples describe photographic elements in which our colored materials are added to hydrophilic colloid layers (sensitized or not), it is to be understood that one, two or three of our colored materials are also advantageously incorporated in the transparent support used in our color elements, or alternatively part or all of one or more of the colored materials required according to our invention are advantageously incorporated in the support while the other colored materials required are advantageously incorporated in one or more of the hydrophilic colloid layers.

The following example illustrates a photographic material in which the cyan and magenta dye density deficiency is substantially eliminated by incorporation of a single pigment into the hydrophobic support layer of the material.

EXAMPLE 8 A color negative film E is made identical to color negative film A described in Example 6 excepting that the transparent support used is cellulose acetate containing Phthalocyanine Blue pigment incorporated in it so that there is 13 mg. of the pigment/ft. of the support. This support is prepared by intimately blending into a cellulose acetate coating dope a composition containing 2% of a dispersion of Phthalocyanine Blue in cellulose acetate (1:1) and 2% cellulose acetate cotton dissolved in 90/ 10 ethylene dichloride/methanol. Color negative film E is exposed to the same original light image and under the same conditions used to expose color negative film A in Example 6. Using the same procedures, processes and color intermediate film used in Example 6, color negative E is used to make intermediate color positive E, and duplicate color negative E. Color print film is exposed to color negative E interspliced with duplicate color negative E using exposure conditions balanced for color negative film E and the color print film. The processed color positive material gives good reproduction of the Original light image whether it is exposed from the color negative E or duplicate color negative E. Example 6 shows that color negative A requires a different exposure condition than duplicate color negative A to give good reproduction of the original light image.

Although the examples show the incorporation of our colored materials in the color negative material, it is to be understood that alternatively our colored materials are advantageously used according to our invention in the color intermediate material instead of in the color negative material.

It is to be understood that in those products which contain incorporated colored color-forming couplers as well as uncolored color-forming couplers that the ratio of the amount of colored color-forming coupler to the amount of uncolored color-forming coupler is fixed by the correction needed to eliminate the unwanted light absorption of the image dyes and therefore additional colored color-forming couplers cannot be added in place of our colored materials to correct for deficiencies in the D-min.

Although the illustrated examples given use only silver bromoidide gelatin emulsions, it is understood that any of the light-sensitive silver halides may be used, emulsified in any of the hydrophilic colloid materials used in photographic layers in place of gelatin.

Our colored materials are advantageously incorporated in any of the known multicolor photographic materials according to our invention. In color reversal materials where oftentimes the color process provides no means for correcting for a dye deficiency in the minimum density area without producing unacceptable changes in the color balance of the midtone and maximum density portions of the image use of our invention advantageously corrects for the dye deficiency. In color materials, such as color negative film, our invention is advantageously used to make color negatives that can be intercut With duplicate color negatives to produce color positives without the usual changes in printing (exposure) conditions in changing from color negative to duplicate color negative. It can, therefore, be seen that use of our photographic materials produce valuable technical advances in the art of color photography.

The azomethine dyes of Formula I (illustrated by colored materials 4, 5 and 6), Formula II (illustrated by colored materials 14 through 17) and the indoaniline dyes of Formula III (illustrated by colored material 11), Formula IV (illustrated by colored material are well known in the art and are prepared by reacting the corresponding open-chain, pyrazolone, phenolic and naphthoic couplers in aqueous, alkaline solutions (or dispersions) with well-known oxidized primary aromatic amino color developing agents. The dyes formed by these reactions are separated by filtration and washed in water or other suitable solvent to remove the unused coupler and/or oxidized developing agent.

Colored material 1 is prepared to advantage by reacting 1 molar equivalent of the diazonium salt of 2,2- disulfo-4,4-diamino stilbene with 2 molar equivalents of 4-propyloxyaniline. Colored materials 2 and 3 are available commercially under the trademark Padding Yellow GL of the Textile Colors Division, Interchemical Corporation. Colored materials 7, 8, 9 and 12 are well known and are available commercially. Colored material 13 is made by reacting 1 molar equivalent of the diazonium salt of 4,4 diamino 2,2',5,5' tetramethyl triphenylmethane with 2 molar equivalents of 8-amino-2-N- heptoyl I-I Acid.

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

We claim:

1. In a multicolor photographic element comprising a support having coated thereon dispersions of (1) redsensitized silver halide grains, (2) green-sensitized silver halide grains and (3) blue-sensitive silver halide grains in hydrophilic colloid, which produces a multicolor image reproduction that has a deficiency in the minimum density areas of at least one of the image dyes forming the multicolor image, the improvement comprising the incorporation in the said element of at least one nonimage-recording colored material that is nondifiusible and nonbleachable, so that for each of said image dyes that is deficient in dye density in the minimum density areas of the said image, there is incorporated one of said colored materials having its maximum light absorption at about the same wavelength as the maximum light absorption of the said image dye that is deficient in its minimum density areas, a sufficient amount of each of said colored materials being incorporated to produce a density of up to about 0.3 density units that substantially eliminates each image dye deficiency in the minimum density area of the image.

2. A multicolor element of claim 1 which the said red-sensitized silver halide grains, the said green-sensitized silver halide grains and the said blue-sensitive silver halide grains are coated in different layers on the said support.

3. A multicolor element of claim 1 in which the said colored material is selected from the class consisting of dyes and pigments that have no appreciable eifect on the sensitivity of the said silver halide grains.

4. In a multicolor, multilayer color film comprising a support layer having coated in succession thereon a dispersion of red-sensitized silver halide grains in a hydrophilic colloid layer, a dispersion of green-sensitized silver halide grains in a hydrophilic colloid layer and a dispersion of blue-sensitive silver halide grains in a hydrophilic colloid layer which produces a multicolor image reproduction that has a deficiency in the minimum density areas of at least one of the image dyes forming the multicolor image, the improvement comprising the incorporation in at least one of the said layers of nonimagerecording colored material that is nondiifusible and nonbleachable and has its maximum light absorption at about the same wavelength as the maximum light absorption of the said image dye which is deficient in dye density in the minimum density areas of the image, a sufficient amount of said colored material being incorporated to produce a density of up to about 0.3 density units to substantially eliminate the image dye deficiency in the minimum density areas of the image.

5. A multicolor, multilayer color film of claim 4 in which the said colored material has substantially no effect on the sensitivity of the said silver halide grains and is selected from the class consisting of cyan-colored dyes, magenta-colored dyes, yellow-colored dyes, cyancolored pigments, magenta-colored pigments and yellowcolored pigments.

6. A multicolor, multilayer color film of claim 4 in which the said nonimage-recording colored material is selected from the class consisting of: indigo, Phthalocyanine Blue (Color Index 74160); 2-[6-(2,4-di-tert.-amylphenoxy)butylcarbamyl] 1,4 [p-(N,N-diethylaminophenyl)]naphthoquinone monoimine; and 2-{4 [oi-(4"- tert. amylphenoxy) n butylamino]benzoylamino}-1, 4-[p (N,N diethylaminophenyl)]quinone monoimine; said colored material being incorporated in the said dispersion of red-sensitized silver halide grains.

7. A multicolor, multilayer color film of claim 4 in which the said nonimage-recording colored material is selected from the class consisting of: thioindigo; 2,2',5, tetramethyltriphenylmethane 4,4 bis(azo-2-N- heptoyl H Acid); 1 (2,4,6 trichlorophenyl) 3 {3-[oc- (2,4 di tert amylphenoxy)acetamido]benzamido}-4- (4 N,N diethylaminophenylimino) 5 pyrazolone; 1 (2,4,6 trichlorophenyl) 3 (4 nitroanilino)-4- (4 N ethyl N fi methanesulfonamidoethyl)aminophenylimino 5 pyrazolone; 1 (2,6 dichloro 4- cyanophenyl) 3 (2,4 dichloroanilino) 4 (4N,N- diethylaminophenylimino) 5 pyrazolone; and 1 (2,4- dichloro 4 nitrophenyl) 3 (2,4 dichloroanilino)- 4-(4 N,N diethylaminophenylimino) 5 pyrazolone; said colored material being incorporated in the said dispersion of green-sensitized silver halide grains.

8. A multilayer reversal color film comprising a trans parent film support coated in succession on one side with a red-sensitized silver bromoiodide gelatin emulsion containing incorporated phthalocyanine blue pigment coated at about 20 milligrams per square foot, a greensensitized silver bromoiodide gelatin emulsion and a blue sensitive silver bromoiodide gelatin emulsion.

9. A multilayer reversal color film comprising a transparent film support coated in succession on one side with a red-sensitized silver bromoiodide gelatin emulsion, a green-sensitized silver bromoiodide gelatin emulsion containing about 0.9 milligram per square foot of the magenta dye 2,2,5,S tetramethyl triphenylmethane-4, 4-bis-(azo-2-N-heptoyl H Acid), and a blue-sensitive silver bromoiodide gelatin emulsion.

10. A multilayer reversal color film comprising a transparent film support coated in succession on one side with a red-sensitized silver bromoiodide gelatin emulsion, a green-sensitized silver bromoiodide gelatin emulsion, and a blue-sensitive silver bromoiodide gelatin emulsion containing about one milligram per square foot of the yellow dye 2,2 disulfo 4,4 bis-(p-propyloxyphenylazo)stilbene.

11. A multilayer reversal color film comprising a transparent film support coated in succession on one side with a red-sensitized silver bromoiodide gelatin emulsion, a green-sensitized silver bromoiodide gelatin emulsion, and a blue-sensitive silver bromoiodide gelatin emulsion containing about 3 milligrams per square foot of the yellow dye 4,4 bis [0t (phenylcarbamyD-u- (acetyl -methylazo] -3 ,3 -dichlorobiphenyl.

12. A multicolor, multilayer color film of claim 4 in which the said nonimage-recording colored material is selected from the class consisting of: 2,2 disulfo-4,4'- bis (p propyloxyphenylazo)stilbene; 4,4 bis[u- (phenylcarbamyl a (acethyl)methylazo] 3,3 dichlorobiphenyl; 4,4 bis [a (o tolylcarbamyD-a- (acetylmethylazo)] 3,3 dichlorobiphenyl; a pivalyla [4 (N ethyl N ,8 methanesulfonamidoethyl) aminophenylimino} acetanilide; u {3 [7 (2,4 ditert amylphenoxy)butyramido]benzoyl} o. [4 (N,N- diethylaminophenylimino)] 2 methoxyacetanilide; a- (2 ethoxy)benzoyl on [4 (N-ethyl N fi methanesulfonamidmoethyl)aminophenylimino] 3 ['y (2,4- di tert amylphenoxy)butyramido]acetanilide; and indanthrene yellow GK.

13. In a multicolor, multilayer color film comprising a support layer having coated in succession thereon a dispersion of red-sensitized silver halide grains and a cyan-dye-forming coupler in a hydrophilic colloid layer, a dispersion of green-sensitized silver halide grains and a magenta-dye-forming coupler in a hydrophilic colloid layer, and a dispersion of blue-sensitive silver halide grains and a yellow-dye-forming coupler in a hydrophilic colloid layer which produces a multicolor image reproduction that has deficiency in the minimum density areas of at least one of the image dyes forming the multicolor image, the improvement comprising the incorporation in the said film of at least one nonimage-recording colored material that is nonditfusible and nonbleachable, so that for each of said image dyes that is deficient in dye density in the minimum density areas of the said image, there is incorporated one of said colored materials having its maximum light absorption at about the same wavelength as the maximum light absorption of the said image dye that is deficient in its minimum density areas, a sufficient amount of each of said colored materials being incorporated to produce a density of up to about 0.3 density units that substantially eliminates each image dye deficiency in the minimum density area of the image.

14. A multicolor, multilayer color film of claim 13 in which is incorporated a suflicient amount of a nonimagerecording cyano-colored material, a sufficient amount of a nonimage-recording magenta-colored material, and a sufficient amount of a nonimage-recording yellow-colored material in the said red-sensitized, green-sensitized and blue-sensitive layers, respectively, to compensate for the image dye deficiency in the respective minimum density areas of the image.

15. A multicolor, multilayer color film of claim 13 that has incorporated in the red-sensitized layer enough phthalocyanine blue pigment to produce a cyan density of about 0.3, that has incorporated in the green-sensitized layer enough 2,2'-5,5'-tetramethyltriphenylmethane-4,4- bis-(azo-Z-N-heptoyl H Acid) to produce a magenta density of about 0.2, and that has incorporated in the bluesensitive layer enough 4,4-bis-[or-(phenylcarbamyl)a- (acetyl)methylazo]-3,3'-dichlorobiphenyl to produce a yellow density of about 0.1 so that the deficiencies in the minimum density areas of the respective dye images are substantially eliminated.

16. A multicolor, multilayer color film of claim 13 in which there is a hydrophilic colloid layer between the said support layer and the said red-sensitized layer, a hydrophilic colloid layer between the said red-sensitized layer and the said green-sensitized layer and a hydrophilic colloid layer between the said green-sensitized layer and the said blue-sensitive layer, and the nonimage-recording cyan-colored material needed to compensate for the deficiency in the minimum density of the cyan-image is incorporated in at least one of (1) the support layer, (2) the hydrophilic colloid layer between the support layer and the red-sensitized layer and (3) the red-sensitized layer, and the nonimage-recording magenta-colored material needed to compensate for the deficiency in the minimum density of the magerfta image is incor* porated in at least one of (1) the hydrophilic colloid layer between the red-sensitized layer and the green-sensitized layer and (2) the green-sensitized layer, and the nonimage-recording yellow-colored material needed to compensate for the deficiency in the minimum density of the yellow image is incorporatedin at least one of (1) the hydrophilic colloid layer between the green-sensitized layer and the blue-sensitive layer and (2) the blue-sensitive layer.

17. A multilayer reversal color film comprising a transparent cellulose acetate film support containing incorporated Phthalocyanine Blue, said support being coated in succession on one side with a red-sensitized silver bromoiodide gelatin emulsion, a green-sensitized silver bromoiodide gelatin emulsion and a blue-sensitive silver bromoiodide gelatin emulsion, said support containing sufiicient incorporated Phthalocyanine Blue to produce a density of up to about 0.3 density units that substantially eliminates a dye deficiency in the D-min. of said color film when color processed.

18. A multilayer reversal color film of claim 17 containing about 13 mg. of Phthalocyanine Blue per ft.

19. A multilayer reversal color film comprising a transparent film support layer coated with a red-sensitized silver halide emulsion layer, a green-sensitized silver halide emulsion layer and a blue-sensitive halide emulsion layer, said film containing incorporated in at least one of said layers at least one nonimage-recording colored material that is nondiffusible and nonbleachable selected from the class consisting of indigo: Phthalocyanine Blue (Color Index 74160)s 2-[6-(2,4-di-tert-amylphenoxy)-butylcarbamyl] 1,4 [p-(N,N-diethylaminophenyl]naphthoquinone monoimine; and 2 {4-[a(4-tertamylphenoxy) n butylamino1benzoylamino} 1,4-[p- (N,N-diethylaminophenyl)]quinone monoimine; thioindigo; 2,2',5,5 tetramethyltriphenylmethane-4,4-bis(azo- Z-N-heptoyl H Acid); 1-(2,4,6-trichlorophenyl)-3{3-[a- (2,4 di tert-amylphenoxy)acetamido]benzamido}-4-(4- N,N-diethylaminophenylimino) 5 pyrazolone; 1-(2,4,6- trichlorophenyl) 3 (4-nitroanilino)-4-(4-N-ethyl-N-;3- methanesulfonamidoethyl)aminophenylimino] 5 pyrazolone; 1 (2,6-dichlro-4-cyanophenyl)-3-(2,4-dichloroanilino)-4-(4-N,N diethylaminophenylimino)--pyrazolone; and 1-(2,4-dichloro-4-nitrophenyl)-3-(2,4-dichloroanilino)-4-(4-N,N diethylaminophenylimino)-5-pyrazolone; 2,2'-disulfo-4,4'-bis-(p-propyloxyphenylazo)stilbene; 4,4'-biS[x (phenylcarbamyl)-a-(acetyl)methylazo]-3,3'- dichlorobiphenyl; 4,4-bis-[a(o-tolylcarbamy1)-a-(acetyl methylazo1-3 ,3'-dichlorobiphenyl; a-pivalyl-a- [4- N-ethyl-N B methanesulfonamidoethyl)aminophenylimino1- acetanilide; oc-{3-['y-(2,4-di tert amylphenoxy)butyramido benzoyl}-a- [4- N,-N diethylaminophenylimino) Z-methoxyacetanilide; oc- Z-ethoxy) benzoyl-a- [4- N-ethyl-N-fi methanesulfonamidoethyl)aminophenylimino1-3- ['y- 2,4-di-tert-amylphenoxy) butyramido] acetanilide; and indanthrene yellow GK; so that this is a sufficient amount of said colored material incorporated to produce a density of up to about 0.3 density units.

References Cited UNITED STATES PATENTS 3,114,634 12/1963 Brown 96-99 3,177,078 1/ 1963 Bockly 9674 NORMAN G. TORCHIN, Primary Examiner J. R. HIGHTOWER, Assistant Examiner US. Cl. X.R. 9672