Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
  • G03C1/83—Organic dyestuffs therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
  • G03C1/83—Organic dyestuffs therefor
  • G03C1/832—Methine or polymethine dyes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/18—Processes for the correction of the colour image in subtractive colour photography

Definitions

• 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.
• 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.
• 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.
• 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.
• 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.
• the sensitometric curves for the three dye images should be identical.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• dyes used to advantage according to our invention include 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.
• pigments used to advantage according to our invention include the phthalocyanines; the benzidine textile colors and diazo-substituted triphenyl methanes.
• 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.
• 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-s
• 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)
• 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.
• 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).
• 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-a
• 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.
• 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.
• colloidal albumin colloidal albumin
• a cellulose derivative a cellulose derivative
• synthetic resin for instance, a polyvinyl compound.
• 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.
• 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.
• 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.
• unbleachable we mean that they are not decolorized by the processing solutions used in color processmg.
• 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.
• 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.
• the exposed Coatings 1 and 2 of Example 1 are processed through the following steps:
• 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.
• 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.
• the cyan-colored material 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.
• the minimum density of the developed image has a deficiency in yellow dye
• 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.
• 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.
• 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.
• our Coating 8 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.
• 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.
• 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.
• magentacolored dye or pigment 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.
• magentacolored materials can be used according to our invention including colored materials 12 through 17 and other dyes of Formula II.
• 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.
• 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.
• 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-(acety
• 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.
• 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).
• a color negative film identified as C 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 support 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
• 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).
• 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.
• 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.
• 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.
• 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.
• our colored materials are advantageously incorporated in any of the known multicolor photographic materials according to our invention.
• 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.
• 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.
• 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.
• 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.
• 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
• 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.
• 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.
• 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.
• 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.
• 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.
• 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
• 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.
• 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.
• 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.
• a multilayer reversal color film of claim 17 containing about 13 mg. of Phthalocyanine Blue per ft.
• 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

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• 1968
  • 1968-01-02 US US694851A patent/US3547640A/en not_active Expired - Lifetime
  • 1968-03-07 GB GB01013/68A patent/GB1214056A/en not_active Expired
  • 1968-03-08 DE DE19681622929 patent/DE1622929A1/de active Pending
  • 1968-03-11 FR FR1557288D patent/FR1557288A/fr not_active Expired
  • 1968-03-11 BE BE712021D patent/BE712021A/xx unknown

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