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
  • 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
• • 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
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials

Definitions

• the present invention relates to a method for producing integral correction masks during the processing of multilayer color material and to the masked film thus obtame
• yellow, magenta and cyan dye images are produced in the blue, green and red sensitive layers, respectively, of multilayer material by the method known as color development.
• This method involves the development of developable multilayer material with a primary aromatic amino developer in the presence of color formers while causing the formation in situ with the developed silver images of a yellow azomethine dye image in the blue sensitive layer, a magenta azomethine dye image in the green sensitive layer and a cyan quinonimine dye image in the red sensitive layer.
• An ideal yellow dye should transmit green and red; an ideal magenta, blue and red; and an ideal cyan, blue and green light completely. Most yellow dyes are quite satisfactory but the magenta dyes as a rule are deficient in their blue transmission and the cyans deficient in both blue and green. Thus if these three subtractive color images were superimposed in an integral tripack, it is manifest that the blue portion of the exposing light would be modulated by all three dye images instead of the yellow image only, and the green portion of the exposing light would be modulated by the cyan image as well as the magenta image.
• the so-called masking technique is used. If a positive yellow image of correct density and gradation be superimposed in exact register with the negative magenta image (e. g., maximum density of yellow masking image should be equal to the blue absorption of the magenta dye at maximum density), it would appear, when the combined images are examined through a blue filter, as if the magenta dyestutf image possessed identical blue transmission in both low and high density regions. Similarly, a red positive masking image would correct for the deficient blue and green transmission characteristics of the negative cyan quinonimine dye image.
• azo linkages are sometimes displaced rather slowly and incompletely during the color development step, and therefore it is difficult to obtain azomethine (quinoneimine) color images and corresponding masking images of satisfactory density and contrast during the usual processing time.
• my invention in its broadest aspects envisages the formation of the color masks by correlating with the usual processing of multilayer material by the color forming development method of a diazo coupling step usually effected subsequent to fixing.
• my invention serves to produce masks of the desired color, density and gradation by controlling the following factors, to wit:
• the diazonium compound which is utilized for coupling with residual color former to produce the azo dye masks may be derived from any of the aromatic amines generally employed in the manufacture of azo dyes.
• aromatic amines generally employed in the manufacture of azo dyes.
• examples of such amines are aniline, sulfanilic acid, metanilic acid, 3-chloro-aniline, 2,5-dichloroaniline, o-anisidine, p-toluidine, o-nitroaniline, p-anisidine, o-toluidine, p-nitroaniline, Z-chloroaniline, 4-nitro-2-methoxy aniline, 4-benzoylamino-2,S-diethoxy aniline, p-diethylamino aniline, S-methyl-Z-methoxy aniline, 2-methyl-4-nitroaniline, 4-chloro-2-methyl aniline, l-naphthylamine, 4-chloro-2- nitroaniline, and the like
• the formation of the diazonium compound from the aforesaid amines follows the customary practice of diazotizing the amine with sodium nitrite and an inorganic acid at low temperatures followed by bufi'ering of the diazonium salt solution to the appropriate pH with a suitable buflfering agent such as sodium acetate.
• diazonium salts are alike in their coupling potentials.
• sulfanilic acid or p-nitroaniline which contains an electronegative substituent in the molecule yield diazonium salts having high coupling potentials and which undergo coupling reactions in solutions buffered to a relatively low pH.
• diazonium salts containing electropositive substituents such as those derived from p-anisidine or p-diethylamino aniline, have lower coupling potentials and undergo the diazo coupling reaction only in media which are buffered to a higher pH than the above. It is therefore possible to vary the density and gradation of the masking images by selecting the appropriate color former and by adjusting the coupling time and the pH of the diazonium salt solution.
• the color formers which yield satisfactory yellow azomethine dye images on color forming development are those of the acylacetanilide type having the following general formula:
• R is an aromatic radical such as phenyl, acylaminophenyl, i. e., stearylaminophenyl, lauroylaminophenyl, aminophenyl, i. e., decylaminophenyl, octadecylaminophenyl, and the like, alkyl radical such as methyl, ethyl, lauryl, stearyl, and the like, and R is an aromatic radical as above, or alkyl suchas stearyl, lauryl, myristyl, and the like. Color formers within this class will couple 5 readily with most diazonium salts only if the pH be greater than 6.
• color formers which contain replaceable groups in the coupling position such as sulfonic acid groups or halogen atoms, i. e., chlorine or bromine, are not affected by diazonium salts, but yield azomethine or quinonimine dye images due to the displacement of the substituent in the coupling position by the oxidized developer.
• the color formers not substituted in the coupling position readily couple with diazonium compounds to yield azo dyes. This finding is better illustrated by the following reactions involving oc-hydroxy naphthoic acid amide couplers, on the one hand, and pyrazolone couplers on the other hand.
• An alternative or supplemental method of controlling the formation of the yellow azo masking image in the green sensitive layer involves a controlled blocking of the coupling position of the pyrazolone color former which contains no replaceable substituent.
• an aldehyde solution such as formaldehyde, glyoxal, etc.
• the coupling ability of the pyrazolone color former with diazonium salts is reduced depending upon the time of treatment. This result is apparently due to the formation of a non-displaceable methylene group between two molecules of the pyrazolone or between the pyrazolone and the gelatine according to the following equation:
• the photographic material which is to be subjected to the processing contemplated herein may be constructed as follows: On a film base there is cast a red sensitive silver halide emulsion layer containing a mixture of two cyan color formers, one of which contains a replaceable group, such as sulfo or halogen, in the coupling position, and the other of which is free from such substituent.
• the color formers employed in the red sensitive bottom layer are preferably a-hydroxy naphthoic acid amides containing a radical rendering the color formers fast to diffusion, preferably a radical having a carbon chain of at least 12 carbon atoms.
• the green sensitive silver halide emulsion layer cast upon the separation layer contains a mixture of two magenta color formers, one of which contains a replaceable substituent in the coupling position, such as sulfo, and the other of which is free from such substituent.
• the magenta color formers are preferably of the pyrazolone class containing a radical as of the above type, rendering them fast to diffusion in the emulsion layer.
• a filter layer which may be of colloidal silver or a dischargeable yellow dye, and over the filter layer is cast a blue sensitive silver halide emulsion layer containing a yellow color former which is preferably an acylacetanilide containing a radical of the aforementioned type, rendering the compound fast to diffusion in the emulsion.
• yellow color formers of the aforestated class which I have found to be effective not only for u the development of the yellow azomethine dye image (3) 1 (3 carboxyphenyl) 3 heptadecyl 5 pyrazolone-4-sulfonic acid.
• cyan color formers containing no replaceilble substituent in the coupling position are the folowing:
• cyan color formers containing a replaceable substituent in the coupling position are the following:
• the multilayer material is color developed with a primary aromatic amino developer such as a p-diethylaminoaniline after which it is short-stopped, bleached with a ferricyanide solution, fixed in hypo, and then submitted to a masking solution containing a. diazonium salt bufiered to the proper pH, i. e., approximately 5, by the addition of sodium acetate.
• a primary aromatic amino developer such as a p-diethylaminoaniline
• ferricyanide solution fixed in hypo
• the material is finally washed, yielding a negative containing in the appropriate layers negative yellow, magenta and cyan dye images, the layers bearing the magenta and cyan images also containing a positive yellow and red printing mask respectively.
• Processing of color reversible material constituted as above may be effected as follows: After exposure the film is developed in a black and white developer such as Metol-Hydroquinone short-stopped, re-exposed, and color-developed as above. The film is then subjected to a clearing bath after which it is bleached in a ferricyanide solution, fixed, and then subjected to the masking solution containing the diazonium salt properly buflfered with sodium acetate. In this case the color developed images are positives and the printing masks negatives.
• a black and white developer such as Metol-Hydroquinone short-stopped, re-exposed, and color-developed as above.
• the film is then subjected to a clearing bath after which it is bleached in a ferricyanide solution, fixed, and then subjected to the masking solution containing the diazonium salt properly buflfered with sodium acetate.
• the color developed images are positives
• Example I A photographic multilayer material constructed as previously outlined and containing in th blue sensitive top layer as the yellow color former, 3-[p-stearoylaminobenzoylacetamido]-isophthalic acid, in the green sensitive layer as the magenta color former, a mixture of 1 (4'phenoxy 3' sulfophenyl) 3 heptadecyl 5- pyrazolone and l-phenyl-3-heptadecyl-5-pyrazolone-4- sulfonic acid, and in the red sensitive layer as the cyan color former a mixture of l-hydroxy-Z-naphthoyl-N- octadecylamide-4-sulfonic acid and l-hydroxy-Z-naphthoyl-2'-N-methyloctadecylamino-5'-sulfoanilide is exposed and then processed as follows:
• Step 1 Color developmentl5 minutes (20 C.).
• Step 2 Short stop--1 minute.
• Step 3 Harden4 minutes (20 C.).
• Step 4 Wash-10 minutes.
• Step 5 Bleach5 minutes (20 C.).
• Step 6 Wash-3 minutes.
• Step 7 Fix-5 minutes (20 C.).
• Step 8 Wash5 minutes.
• Step 9 Masking solution2 to 5 minutes (20 C.).
• sulfanilic acid (monohydrate) is dissolved in 500 parts of warm water. The solution is cooled quickly to 5 C., acidified with 1.5 parts of concentrated hydrochloric acid and diazotized with 0.7 part of sodium nitrite in 25 parts of water. The pH of the diazonium salt solution is adjusted to approximately by the addition of .4 part of sodium acetate (trihydrate) Step Washminutes.
• the completely processed film contains negative yellow and magenta azomethine dye images in the blue and green sensitive layer and a cyan quinonimine dye image in the red sensitive layer in combination with positive yellow and red azo dye masking images in the green and red sensitive layers respectively. No mask is formed in the blue sensitive layer.
• Example II A color reversible multilayer material constructed as in Example I is exposed and processed as follows:
• Step 1 Primary silver development-12 minutes Water cc 750. Metol g 3.0 Sodium sulfite (anhydrous) g 50.0 Sodium carbonate (monohydrate) g 40.0 Sodium thiocyanate g 2.0 Potassium bromide g 2.0
• Step 2 Short stop3 minutes (20 C.).
• Step 3 Wash1 minute.
• Step 4 Second exposure.
• Step 5 Color development18 minutes (20 C.).
• Step 6 Clearing bath-3 minutes (20 C.).
• Step 7 Harden5 minutes (20 C.).
• Step 12 Wash-5 minutes.
• Step 13 Masking solution3 to 5 minutes (20 C.
• the film contains positive azomethine dye images in the blue and green sensitive layer and a positive cyan quinonimine dye image in the red sensitive layer in combination with negative yellow and red azo dye images in the green and red sensitive layers respectively. As in Example I, no masking image is produced in the blue sensitive layer.
• Example 111 The coated material and procedure is the same as in Example I excepting that the color former, 1-phenyl-3- heptadecyl-5-pyrazolone-4-sulfonic acid is omitted. In this case, the material is bathed after Step 8 in the following solution for a predetermined period of time ranging from 15 seconds to 5 minutes:
• Example IV The procedure is the same as in Example 11 excepting that after Step 12, the film is bathed in the formaldehyde solution of Example 111 for a period of time ranging from 15 seconds to 5 minutes. As noted in Example 111 this provides an additional or alternative control in the masking treatment.
• my invention contemplates the masking of both the magenta and cyan color developed images, while insuring careful control of the color density and gradation of the masking images. It is to be understood, however, that my invention embraces generally the formation of masks in the processing of color film by the color forming development method while utilizing the diazo procedure, and more particularly the use of such procedure for the selective formation of the masks in the layers desired.
• a mask is desired in only the magenta layer without specific regard to the density and gradation of the mask, this may be effected by proceeding as above but while utilizing in the blue sensitive layer an acylacetanilide as heretofore described, in the green sensitive layer a single pyrazolone as heretofore mentioned having no replaceable substituent in the coupling position, and in the red sensitive layer a single a-naphthoic acid amide as heretofore described containing a. replaceable substituent in the coupling position.
• a diazonium salt solution as contemplated herein, when buffered to a pH below 6, will yield only a yellow mask in the green sensitive layer.
• the single pyrazolone color former in the green sensitive layer will contain a replaceable substituent in the coupling position and the single a-naphthoic acid coupler in the cyan layer will contain no substituent in the coupling position.
• a red azo dye mask will be formed only in the red sensitive layer.
• the green sensitive layer would contain only a single color former in which the coupling position is blocked.
• the red sensitive layer would contain a mixture of color formers of the type required by the examples.
• magenta color formers may be a mixture of any of those mentioned so long as the mixture contains a pyrazolone with a substituent in the coupling position and a pyrazolone free from a substituent in such position.
• the slaame is also true of the various cyan color formers listed a ove.
• the ratio of substituted to unsubstituted color formers must be determined empirically because the characteristics of the masking images depend on many factors: such as, diazo coupling rate, color former concentration, etc. For example, in one set of experiments it has been found that good results are obtained if the unsubstituted and substituted naphthoic acid amides are present in a ratio of (1:1). It appears that the ratio may be as high as 11 (10:1) or as low as (1:10) depending on the desired density and gradation of the masked images.
• diazonium salt there may be employed any of those referred to herein in lieu of that derived from sulfanilic acid.
• the cyan, yellow and magenta color formers may be incorporated in the blue, green and red sensitive layers respectively of the multilayer material which is to be masked; it is to be understood, however, that if the original object is to be rendered in true color, the modified masked transparency must be exposed onto a printing material in which the magenta, cyan and yellow color formers are incorporated in the blue, green and red sensitized layers respectively.
• This invention therefore pertains to the method by which the dye images produced during color development can be corrected for their imperfect spectral characteristics, and is not restricted to any specified arrangement of the color formers in the sensitized layers or to any specified position of the layers in respect to each other.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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  • BE BE497011D patent/BE497011A/xx unknown
  • US US2733143D patent/US2733143A/en not_active Expired - Lifetime
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  • 1949-07-16 US US105267A patent/US2704709A/en not_active Expired - Lifetime
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  • 1950-06-19 FR FR1020511D patent/FR1020511A/fr not_active Expired
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