US2848326A - Method for preparing masked images - Google Patents

Method for preparing masked images Download PDF

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Publication number
US2848326A
US2848326A US536502A US53650255A US2848326A US 2848326 A US2848326 A US 2848326A US 536502 A US536502 A US 536502A US 53650255 A US53650255 A US 53650255A US 2848326 A US2848326 A US 2848326A
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United States
Prior art keywords
image
negative
silver
coupler
silver halide
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Expired - Lifetime
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US536502A
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English (en)
Inventor
Keith E Whitmore
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Priority to BE551200D priority Critical patent/BE551200A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US536502A priority patent/US2848326A/en
Priority to GB25722/56A priority patent/GB826493A/en
Priority to FR1161137D priority patent/FR1161137A/fr
Application granted granted Critical
Publication of US2848326A publication Critical patent/US2848326A/en
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    • 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
    • G03C7/32—Colour coupling substances
    • G03C7/333—Coloured coupling substances, e.g. for the correction of the coloured image
    • G03C7/3335—Coloured coupling substances, e.g. for the correction of the coloured image containing an azo chromophore

Definitions

  • a common method for correcting the above kind of defects in reproductions includes the making of a separate masking image, generally a thin lowcont-rast positive if printing from a neg-a tive transparency, registering the resultant mask with the transparency, and then printing the final reproduction through the combination.
  • the transparency obtained contains in the colored coupler layer a diffuse or unsharp mask image which functions in a printing operation to increase the contract in microstructure relative to extended area, and also acts to improve the overall image sharpness of the reproduction.
  • the thickness of the gelatin interlayer is a functionof the degree of unsharpness which should be corrected in the principal image, i. e. the thicker the layer the more diffuse or unsharp is the masking image formed and may vary from 1 to 15 microns for use with fluorescent screens in radiography to zero (no gelatin interlayer) for use with sharp images as may be encountered in documentary work.
  • the rehalogenated element is then redeveloped in a solution containing a substituted phenylene diamine type of color developer such as N ethyl N-(p-methanesulfonamidoethyl)-3- methyl-4-aminoaniline or N-ethyl-B-methanesulphonamidoethyl-4-aminoaniline and similar developers which are described in U. S. Patent No. 2,193,015, dated March 12, 1940, of A. Weissberger, or such as N-diethyl-p-phenylene diamine, Z-aminod-diethylamino toluene, etc.
  • a substituted phenylene diamine type of color developer such as N ethyl N-(p-methanesulfonamidoethyl)-3- methyl-4-aminoaniline or N-ethyl-B-methanesulphonamidoethyl-4-a
  • the processed element now contains both a negative silver image in the upper layer and in the bottom layer a negative magenta or cyan dye image.
  • the colored coupler employed is such that the negative dye image is soluble, it can be washed out leaving only unchanged coupler which constitutes in this situation a positive yellow or orange colored masking image.
  • the color developer in the developing solution acts in the silver image area to reduce the silver halide to silver and thereby becomes oxidized; (2) the oxidized color developer is then reduced by the hydroquinone sulfonate and the latter thereby becomes oxidized; (3) the oxidized hydroquinone sulfonate and the reduced coupler developer then diffuse through the gelatin interlayer to the bottom layer containing the colored coupler where (4) the oxidized hydroquinone sulfonate oxidizes the reduced color developer in the presence of the colored coupler and (5) the oxidized color developer then couples with the colored coupler to form the dye image.
  • the processing steps for obtaining suitable masked positive images with the described photographic elements ofthe invention require a reversal type of process, but the exposure to the subject is the same regardless of whether the processing is to be negative or reversal.
  • the element is developed to a silver image by use of an ordinary black and white developer solution containing, for example, hydroquinone, N-methyl-p-aminophenol sulfate or a combination of these compounds followed by hardening, bleaching, clearing, flashing, color developing with the previously mentioned phenylene diamine type of color developers, and final washing and drying.
  • the processed element now contains both a positive silver image in the upper layer and in the bottom layer a positive magenta or cyan dye image and an unsharp negative colored coupler image.
  • the formation of the dye masking image is believed to take place in similar manner as previously described for preparing the mentioned masked negative images.
  • an object of my invention to provide a new light-sensitive photographic element which on exposure and processing gives improved masked nega tive and positive images that can be used for superior reproductions. for preparing such masked images, more particularly negative masked images.
  • Another object is to provide a developing solution containing a color developer and a substantial amount of a hydroquinone sulfonic acid or salt thereof.
  • Figs. 1A, Band C and 2A, B and G are enlarged, diagrammatic cross-sectional views of lightsensitive photographic elements before and after processing according to the method of the invention.
  • Fig. 1A shows an element comprising a support 10, a layer 11 attached thereto and containing a yellow or orange colored coupler capable of coupling with the oxidation products of certain primary aromatic amine developing agents to form magenta or cyan colored dyes but containing no silver halide, and a gelatin silver halide emulsion layer 12 superimposed over said layer 11 and containing no coupler compound.
  • the emulsion employed for layer 12 may be one having the usual amount of contrast and capable of being developed to a density range of about 3.0.
  • Fig. 1B shows the element of Fig. 1A after exposure to a subject and complete processing to a masked negative image, the layer 12 now containing a negative silver image 14 and containing no silver halide, and layer 11 now containing a relatively unsharp negative magenta or cyan dye image 15 and a relatively unsharp positive yellow or orange colored coupler image 15a formed by the unchanged colored coupler, in register with the negative silver image 14.
  • Fig. 10 shows the element of Fig. 1A after exposure and complete reversal processing to a masked positive image, the layer 12 now containing a positive silver image 16 and containing no silver halide, and layer 11 now containing a relatively unsharp positive magenta or cyan dye image 17 and a relatively unsharp negative yellow or orange colored coupler image 17a formed by the unchanged colored coupler, in register with the positive silver image 16.
  • Fig. 2A shows an element similar to that of Fig. 1A, except that a relatively thin gelatin layer 13 is interposed between layers 11 and 12.
  • Fig. 2B shows the element of Fig. 2A after exposure and complete processing to a masked negative image, the layer 12 now containing a negative silver image 18 and containing no silver halide, and layer 11 now containing a relatively difiuse or unsharp negative magenta or cyan dye image 19 and a relatively unsharp positive yellow or orange coloredcoupler image 19a formed-by the unchanged colored coupler, in register with the negative silver image 18.
  • Fig. 2C shows the element of Fig. 2A after exposure and complete reversal processing.
  • the layer 12 now containing the positive silver image 20 and containing no silver halide
  • layer 11 now containing a relatively unsharp positive magenta or cyan dye image 21 and a relatively unsharp negative yellow or orange colored coupler image 21a formed by the unchanged coupler, in register with the positive silver image 20.
  • the coupler yields a soluble dye
  • the cyan and magenta images represented by 15, 17, 19 and 21 wash out in processing and leave only the silver and diffuse unchanged colored coupler images 15a, 17a, 19a, and 21a.
  • Suitable colored couplers which couple with the oxidized color developer to give mask dye images include compounds such as the following:
  • This coupler is orange colored and inthe process of the invention it couples with the diffused oxidized color developer to give a soluble cyan dye image.
  • it may be prepared by heating phenyl-l-hydroxy-Z-naphthoate with an excess of ethylene diamine to give the intermediate naphthol compound which is then reacted with rn-chlorocarbonylbenzene sulfonyl chloride, ClCO-C H -SO Cl, in the proportions of two equivalents of the naphthol intermediate to one equivalent of the acid chloride, the amine hydrochloride being separated by filtration.
  • the filtrate is drowned in water and the precipitate collected. This is then refluxed in a 50-50 water and alcohol solution, the excess alcohol removed and the aqueous residue filtered.
  • the filtrate is chilled and the produce collected which has the structure:
  • It may be prepared by heating two equivalents of l -phenyl-3- amino-S-pyrazolone with one equivalent of m-chlorocarbonylbenzene sulfonyl chloride, ClCO-C H -SO Cl, to form the corresponding acid chloride, followed by hydrolysis of the acid chloride to the free sulphonic acid in a 50-50 water and alcohol hydrolysis medium, and then coupling in a basic medium suchas pyridine, sodium hydroxide or acetic acid plus sodium acetate with p-octadecyloxybenzene diazonium chloride to give the colored coupler II.
  • a basic medium suchas pyridine, sodium hydroxide or acetic acid plus sodium acetate with p-octadecyloxybenzene diazonium chloride
  • This'coupler is yellow colored and in the process of the invention it couples with the diffused oxidized color developer to give an isoluble magenta dye image. It may be prepared by heating on a. steam bath a mixture of 1-ptert,-butylphenoxyphenyl-3 amino 5 pyrazolone with alpha-(p-tert. butylphenoxy) propionyl chloride, isolating the amide derivative and then coupling it with pmethoxybenzene diazonium chloride in a basic medium such as pyridine, etc. to give the colored coupler IV.
  • the preferred colored couplers are the compounds III and V.
  • Couplers of the type of above I include 1 hydroxy-N-[B-(3-sulfobenzamido) ethyl] -4- (Z-dodecyloxyphenylazo) -2-naphthamide, i-hydroxy-4-(2-dodecyloxycarbonylphenylazo)3,5' -di carboxy-Z-naphthamide, l-hydroxy-N 3 (3,5-disulfbenzamido)ethyl]-4-(2 dodecyloxycarbonylphenylazo) 2 naphthamide, 1-hydroxy-4-(2-dodecyloxycarbonylphenylazo)-2-(4-sulfonaphthanilide), 1-hydroxy-4-(2-amyloxycarbonyl-3-naphthylazo)-N-[l8 (2 carboxybenzamido)- ethylJ-Z-naphthamide, and the like
  • Suitable hydroquinone sulfonic acids and salts thereof include hydroquinone monosulfonic acid and lithium, sodium, potassium, etc. salts thereof and, hydroquinone disulfom'c acid and mono and dilithium, sodium, potassium, etc. salts thereof.
  • the disulfonates are preferred and particularly potassium hydroquinone disulfonate.
  • the amount of the hydroquinone sulfonic acid compound that is employed in the color developer solution can vary widely, but ordinarily from about 50-200% of the weight of the color developer contained therein is etficacious.
  • Example 1 A photographic element as above described was prepared by first coating a subbed transparent cellulose acetate support of about 0.005" thickness with a gelatin solution in water containing 5.5 g. per 100 cc. of the yellow colored coupler 1-phenyl-3 (2 carboxybenzamido) -4- (4-dodecyloxyphenylazo -5-pyrazolone, designated III above, but containing no silver halide, to a dried thickness of approximately 4 microns, .followed by coating thereover a 5% gelatin solution in water to give a gelatin dried layer approximately 8 microns in thickness, and over this was coated a gelatino-silver bromide emulsion containing no colored coupler and having a cured thickness of approximately 8 microns. The photographic element thus prepared was then exposed to a subject and processed to a masked negative image. The processing solutions and the steps of the process are described in the following:
  • Second developer solution- Benzyl alcohol 4 co. in 800 cc. of
  • Potassium hydroquinone disulionate 2.5 grams. Sodium carbonate (monohydrate).... 50 grams. Sodium hydroxide 0.5 grams Water to make up to a volume of 1 liter.
  • Fixing time 5 mins Washing time. 5 mins Hardening time 3 mins Washing time. 5 mins Rehalogenizing 2 mins Washing time 15mins.
  • the resultant masked negative contains a negative silver image in the upper layer and, since the magenta dye masking image which forms is soluble, it washes out leaving a positive, diffuse yellow image of the unreacted colored coupler in the lower layer adjacent to the support.
  • the masked negative was then printed through a suitable filter onto a fine grain positive film to give on processing a greatly improved positive print as compared with prints obtained with similar unmasked negative transparencies.
  • the desired degree of masking may be controlled by the color of the printing filter.
  • Example 2 A photographic element prepared as described in Example 1 was exposed to a subject and processed to a masked positive image by a reversal process.
  • the processing solutions and the steps of the process are described in the following:
  • Masked positives prepared as described in above Example 2 have special uses. For example, a normal negative may be duplicated and masked at the same time by making use of the described reversal process. Another example is in the preparation of radiographs. As is known, radiographs are customarily viewed and read as negatives. Reversal processing yields a masked positive which will give the conventional radiographic negative in one printing operation. Here also the degree of masking may be controlled by the color of the printing filter.
  • the photographic element can be substituted by other generally similar elements of the invention.
  • the thickness of the gelatin interlayer can be varied from zero to 12 microns.
  • the colored coupler in the lower layer can be replaced by a like amount of any other of the mentioned colored couplers of type I or II which likewise contain solubilizing groups and give similar masked negative and positive images.
  • the colored coupler of the above example is replaced by a colored coupler of the type IV, which contains no solubilizing groups, the masked image obtained also contains an insoluble diffuse magenta image.
  • the cellulose acetate film support can also be replaced by other cellulose 'cstcrs such as cellulose propionate, cellulose acetate-propionate, cellulose acetatebutyrate, etc., by synthetic resins such as polyvinyl acetal, poly esters, etc., by glass and other transparent supporting materials. In special cases a translucent or opaque material can also be used such as paper, metal and the like.
  • the gelatin in the layers may also be replaced by other colloid materials such as polyvinyl alcohol, cellulose carboxylatcs, agar-agar, etc., but gelatin is the preferred colloid material.
  • processing solutions can also be replaced with equivalents.
  • First Developer in the examples can be substituted with either of the following developing compositions:
  • the N-ethyl N-(13-methanesulfonamidoethyl)-3-rnethyl-4- aminoaniline color developer can be substituted, for example, with a like amount of N-diethyl-p-phenylene diamine, or with Z-aminod-diethylamino toluene hydrochloride or with N-ethyl-N-(p-methanesulfonamidoethyl)-4-aminoaniline.
  • the potassium hydroquinone disulfonate can be substituted in the second de- 8 veloper in each of .the examples, with a like amount of any of the mentioned hydroquinone sulfonic acidsand derivatives, for example, with sodium hydroquinone'disulfonate, or with lithium hydroquinone disulfonate or with hydroquinone disulfonic acid to give similarly advantageous masked negatives and positives for reproduction, purposes.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US536502A 1955-09-26 1955-09-26 Method for preparing masked images Expired - Lifetime US2848326A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE551200D BE551200A (en, 2012) 1955-09-26
US536502A US2848326A (en) 1955-09-26 1955-09-26 Method for preparing masked images
GB25722/56A GB826493A (en) 1955-09-26 1956-08-23 A method of making masked photographic images
FR1161137D FR1161137A (fr) 1955-09-26 1956-09-25 Procédé pour la préparation d'images photographiques masquées

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US536502A US2848326A (en) 1955-09-26 1955-09-26 Method for preparing masked images

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GB (1) GB826493A (en, 2012)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3127268A (en) * 1964-03-31 Hellmig
US3135609A (en) * 1960-06-29 1964-06-02 Gen Aniline & Film Corp 1-hydroxy-2-naphthamide couplers for color photography
US3233532A (en) * 1962-04-25 1966-02-08 Minnesota Mining & Mfg Photographic apparatus
US3265502A (en) * 1961-06-21 1966-08-09 Gevert Photo Producten N V Photographic developing compositions
US3411905A (en) * 1965-06-14 1968-11-19 Eastman Kodak Co Photographic masking process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB503824A (en) * 1936-07-07 1939-04-11 Kodak Ltd Process of colour photography
US2306410A (en) * 1936-07-07 1942-12-29 Eastman Kodak Co Color development
US2397452A (en) * 1940-08-01 1946-03-26 Du Pont Photographic element

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB503824A (en) * 1936-07-07 1939-04-11 Kodak Ltd Process of colour photography
US2306410A (en) * 1936-07-07 1942-12-29 Eastman Kodak Co Color development
US2397452A (en) * 1940-08-01 1946-03-26 Du Pont Photographic element

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3127268A (en) * 1964-03-31 Hellmig
US3135609A (en) * 1960-06-29 1964-06-02 Gen Aniline & Film Corp 1-hydroxy-2-naphthamide couplers for color photography
US3265502A (en) * 1961-06-21 1966-08-09 Gevert Photo Producten N V Photographic developing compositions
US3233532A (en) * 1962-04-25 1966-02-08 Minnesota Mining & Mfg Photographic apparatus
US3411905A (en) * 1965-06-14 1968-11-19 Eastman Kodak Co Photographic masking process

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FR1161137A (fr) 1958-08-21
BE551200A (en, 2012)
GB826493A (en) 1960-01-06

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