US3113864A - Reducing fog in reversal color films processed in developers containing couplers - Google Patents

Reducing fog in reversal color films processed in developers containing couplers Download PDF

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US3113864A
US3113864A US819539A US81953959A US3113864A US 3113864 A US3113864 A US 3113864A US 819539 A US819539 A US 819539A US 81953959 A US81953959 A US 81953959A US 3113864 A US3113864 A US 3113864A
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photographic
color
silver halide
halide emulsion
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Barbara C Yager
Catherine M Spath
Judith A Schwan
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/3924—Heterocyclic
    • G03C7/39276—Heterocyclic the nucleus containing nitrogen and sulfur

Definitions

  • This invention relates to color photography, and more particularly, to a method of processing multi-layer color films or papers in such a manner as to reduce color fog and give maximum color density.
  • multi-layer photographic elements used for color photography there are usually three selectively sensitive emulsion layers coated on one side of a single support.
  • the uppermost layer is generally blue-sensitive
  • the next layer is generally green-sensitive
  • the emulsion layer adjacent the support is generally redsensitive.
  • a filter layer for absorbing blue radiation which may be transmitted through the blue-sensitive layer.
  • the multilayer coating can also have other interlayers for specialized purposes. Such multilayer materials have been previously described in the prior art, such as Mannes et al. US. Patent 2,252,718, issued August 19, 1941. Other arrangements of the sensitive layers are also known.
  • Color materials of the type employed in the instant invention are those intended primarily for reversal processes, wherein the exposed material is given a conventional black-and-White development, followed by a reversal exposure, or exposures, and color development.
  • Our invention is particularly useful in processing reversal color materials, wherein the color-forming components or couplers are incorporated in the color developers.
  • an object of our invention to provide an improved method of inhibiting color fog and increasing the maximum color density of reversal color materials intended for processing in color developers containing color-forming materials or couplers. Another object is to provide a method of inhibiting color development fog in the various layers of multilayer color materials.
  • This method consists in contacting the multilayer color material after negative development in the black-and-white developer, but before color development, with an aqueous solution containing certain benzothiazolium or naphthathiazolium salts. This treatment allows normal color development to take place in the exposed layer, but inhibits the development of undesired fog in the unexposed layers.
  • the reversal process used in the present invention is one which has been previously described in the prior art, and it is to be understood that our invention resides in a modification of this prior art technique. That is, it is known that in reversal processing, a colored image can be formed by adding to certain color developing solutions, a compound which couples during development with the oxidation product of the developing agent, thus forming a colored compound which is deposited adjacent to the developed silver halide grains or the silver image, during such color development.
  • the color density improving treatment employed in our invention is applied to the multilayer color material after conventional negative development in a black-and-white developer, and before or after one of the reversal re-exposures for the differentially sensitize demulsion layers.
  • the multilayer color material is, of course, given successive color development treatments for each of the differentially sensitized emulsion layers after reversal reexposure for each emulsion layer.
  • the compounds employed in conjunction with the color developing agents and which couple with the oxidation products of the developing agents during development are generally referred .to as colorforming compounds, or couplers.
  • Such compounds usually belong to one :of three widely known types, i.e., pyrazolone couplers, phenol couplers, and open-chain ketomethylene couplers. These couplers produce, respectively, magenta, cyan and yellow' images.
  • quaternary salts useful in practicing our invention comprise compounds represented by the following general formula:
  • R represents a hydrogen atom or a lower alkyl group, such as methyl, ethyl, etc. (e.g., an .alkyl group containing from 1-2 carbon atoms), R represents a hydrogen atom, an aryl group (e.g., phenyl, 0-, mand p-tolyl, o-, mand p-methoxyphenyl, etc), or an arylenethiazolyl group (e.g., Z-benzothiazolyl, 3-benzothiazolyl, 2 (,3 naphthothiazolyl) etc.)
  • D represents the nonmetallic atoms necessary to complete an aromatic nucleus (e.g., benzene, naphtholene, etc., as well as their substitution products, including such members substituted by methyl, ethyl, methoxyl, ethoxyl, etc.),
  • m represents a positive integer of from 1-26 (provided that
  • a particularly useful group 'of quaternary salts em; braced by Formula I above includes the compounds represented by Ithe following general formula:
  • R, D and X each have the values given above, and m represents a positive integer of from about 126.
  • Typical quaternary salts embraced by Formula I above include the following:
  • the his compounds represented by Formula II can be prepared according to the methods described in Wilson US. Patent 2,425,774, issued August 19, 1947, as well as by the method described by Allen and Wilson US. Patent 2,694,716, issued November 16, 1954.
  • Such methods generally comprise the fusion of a heterocyclic base with an alkylene halide.
  • Alkyl esters of organic sulfonic acids can also be fused with thiazole bases to provide the salts of our invention.
  • the cycloammonium salts useful in practicing our invention are employed in the form of their aqueous solutions.
  • the amount of quaternary salt used in the solutions can be varied, depending upon the particular emulsions employed, the concentration of silver halides in the emulsions, etc. In general, we have found that concentrations of from about 0.25 to 1.0 gram per liter of solution are particularly eifective. However, the most advantageous concentration for a particular color material can be determined by running a series of test strips of silver halide emulsions through a reversal color process of the type described herein, the concentration of the quaternary salt in the treating solution being varied.
  • the multilayer color materials treated in our invention can be immersed in the treating solution, or for continuous processes, the treating solution may be applied, for example, by means of rollers, etc.
  • the multilayer color material it has been found desirable to give the multilayer color material a short washing treatment after treatment with the quaternary salt in order to avoid spotting.
  • the treatment of the multilayer color materials of our invention can be made either before or after the reversal re-exposure step. However, it must be made after the negative development in the black-and-white developer, but before development in the color developer. We have found that the beneficial effects of the quaternary salts of our invention cannot be obtained if these materials are incorporated in the emulsions. In some instances, the thiazolium salt (e.g., Compound 11a) can be incorporated in the color developing solution where it is soluble in such solution.
  • 2,3 62,59 8 (9 2-acetylamino-5 -methylphenol l) 2-benZoylamino-3 ,5 -dimethylphenol l 1 2-u- (p-tert. amylphenoxy -n-butyrylamino--methylphenol 12) 2-11- (p-tert. amylphenoxy) -n-butyrylamino-4-chloro S-methylphenol 13 2- (p'-tert. amylphenoXy-p-benzoyl) amino-4-chloro- 5 -methylphenol 14) 2- 4-tert.
  • amylbenzenesulfonylamino -5- pyrazolone (37) l-phenyl-3- [p- (p'-sec. amylbenzoyl) aminobenzoylamino] -5 -pyr azolone (3 8) 1-m-tolyl-3- [m- ,B-phenylpropionyl aminobenzoylamino] -5-pyrazolone (3 9) 1-m-tolyl-3 2,4-di-tert. butyl-m-tolyloxyacetyl amino) -5-pyrazolone (40) 1- [p- (p'-te1't.
  • Particularly useful color-forming developers comprise those containing primary aromatic amines, containing an amino (substituted or not) or hydroxyl substituent. Phenylenediamines and substituted derivatives thereof containing a primary amino group have been found to provide particularly useful results. Typical of such color-forming developers are the sulfonamido substituted p-phenylenediamines disclosed in Weissberger US. Patent 2,548,574, issued April 10, 1951, the substituted p-phenylenediamines disclosed in Weissberger et a1. U.S. Patent 2,566,271, issued August 28, 1951. Of course, other phenylenediamine color-forming developers can be employed with equal facility in the process of our invention.
  • the first, or negative, developer employed in the process of our invention is generally a rapid developer of the MQ type, i.e., a combination of hydroquinone and Elon (p-N-methylaminophenol) developer, although other high-speed developers, such as those containing Phenidone can also be employed.
  • EXAMPLE 1 A portion of a red-sensitized, gelatino-silver-bromiodide emulsion which had been sensitized with a sulfur compound, a gold compound and a small amount of the oleyl ether of a polyethyleneglycol having a molecular weight of about 900 was coated on a cellulose acetate film support. The coating was then dried and exposed to a step table for second, using a 500-Watt, 3000 K. light source, filtered with a Wratten No. 29 Filter (i.e., a filter transmitting only light from about 610 to 700 millimicrons) and a 0.8 neutral density filter, on an Eastman Type Ib Sensitometer. The exposed coating was then developed for minutes in a developer having the following composition:
  • the coating was washed for 2 minutes with water.
  • the coating was then given a reversal re-exposure seconds flash) with a No. 2 Photofiood Filter with a Lowry red Filter No. 92, set at a distance of about one meter.
  • the coating was developed to an adequate D-max. for minutes in a developer having the following composition:
  • the coating was washed for 10 minutes in water and immersed for 2 minutes in a silver bleach bath having the following composition:
  • the coating was then washed in water for 10 minutes and dried.
  • an identical strip of coating was put through the same process, except that the flash re-exposure was omitted.
  • EXAMPLE 2 In a manner similar to that described above, a multilayer color material was processed both with and without the pre-bath treatment in an aqueous solution containing Compound 1 above (i.e., decamethylene-bisbenzothiazolium perchlorate).
  • the multilayer color material comprised a conventional cellulose acetate film support having coated thereon in order, a gelatin layer, ,a red-sensitized silver halide emulsion layer, a greensensitized silver halide emulsion, a yellow filter layer comprising Carey Lea silver, and a blue-sensitive silver halide emulsion layer.
  • Each of the silver halide emulsion layers was gold and sulfur sensitized as in Example 1, and each contained a small amount of a polyethylene glycol sensitizer having a molecular weight of about 900.
  • EXAMPLE 3 A portion of a blue-sensitive, gelatino-silver-bromiodide emulsion which had been sensitized with a sulfur compound, a gold compound and a polyethyleneglycol sensitizer having a molecular weight of about 900 was coated onto a cellulose acetate support. The coating was then dried and cut into several strips. One strip of the coating was exposed to a step table for A second to a SOO-Watt, 3000 K. light source, filtered with a Wratten No. 49 Filter (i.e., a filter transmitting only light of wavelengths between about 400 and 510 millimicrons) on an Eastman Type Ib Sensitometer. The exposed strip was developed for 10 minutes in a hydroquinone-Elon Developer of the type used in Example 1, and washed for 2 minutes in water.
  • a SOO-Watt, 3000 K. light source filtered with a Wratten No. 49 Filter (i.e., a filter transmitting
  • the strip was given a reversal re-exposure for about 15 seconds (flash) with a No. 2 Photoflood set at a distance of about 1 meter.
  • the strip was then washed, bleached, fixed and washed exactly as described in Example 1 above. In order to determine fog, a duplicate strip was processed, except that the reversal r e-exposure with the Photoflood was omitted.
  • EXAMPLE 4 In exactly the manner described in Example 2 above (i.e., with 12 minutes black-and-white development and with color developer containing 0.5 g. of H-acid), strips of the multilayer color material described in Example 2 were processed, both with and without treatment in one of the pre-baiths containing a quaternary salt.
  • the bromiodide emulsions were sulfur and gold sensitized and contained a polyethyleneglycol sensitizer as described in Example 2.
  • the pre-baths contained 1.0 g./ liter of quaternary salt.
  • the cyan D-rnax. and cyan fog for the film strips are given below:
  • our invention is concerned primarily with treatment of the ordinarily employed gelatino-silver-halide developing-out emulsions. While the examples are concerned primarily with silver bromiodide emulsions, it is to be understood that other silver halide emulsions can be employed, such as silver chloride, 4chlorobromide, -chloroiodide, -chlorobrom iodide and -bromide 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, 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 U.S. Patent 1,574,944, issued March 2, 1926, Sheppard et al. U.S. Patent 1,623,499, issued April 5, 1927, and Sheppard et a l. U.S Patent 2,410,689, issued November 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 U.S. Patent 2,448,060, issued August 31, 1948, and as anti-foggants in higher amounts, as described in Trivelli and Smith U.S. Patents 2,566,245, issued August 28, 1951, and 2,566,263, issued August 28, 1951.
  • the emulsions can also be chemically sensitized with gold salts as described in Waller et al. U.S. Patent 2,399,- 083, issued April 23, 1946, or stabilized with gold salts as described in Damsehroder U.S. Patent 2,597,856, issued May 27, 1952, and Yutzy and Leermakers U.S. Patent 2,597,915, issued May 27, 1952.
  • Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and Z-aurosulfobenzothiazole methochloride.
  • the emulsions can also be chemically sensitized with reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850, issued November 15, 1949), polyamines, such as diethyl triamine (Lowe and Jones U.S. Patent 2,518,698, issued August 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925, issued September 12, 1950), or bis([i-aminoethyl) sulfide and its water-soluble salts (Lowe and Jones U.S. Patent 2,521,- 926, issued September 12, 1950).
  • reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850, issued November 15, 1949), polyamines, such as diethyl triamine (Lowe and Jones U.S. Patent 2,518,698, issued August 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925, issued September 12, 1950), or bis([
  • the emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Patents 1,846,301, issued February 23, 1932; 1,846,302, issued February 23, 1932; and 1,942,- 854, issued January 9, 1934; White U.S. Patent 1,990,507, issued February 12, 1935; Brooker and White U.S. Patents 2,112,140, issued March 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued January 10, 1950, and 2,739,964, issued March 27, 1956; Brooker and Keyes U.S. Patent 2,493,748, issued January 10, 1950; Sprague U.S. Patents 2,503,776, issued April 11, 1950, and 2,519,-
  • Patent 2,666,761 issued January 19, 1954; Heseltine U.S.
  • Patent 2,734,900 issued February 14, 1956; Van Lare U.S.. Patent 2,739,149, issued March 20, 1956; and Kodak Limited British Patent 450,958, accepted July 15, 1936.
  • the emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray U.S. Patent 2,728,663, issued December 27, 1955; Carroll and Murray U.S. Patent 2,728,664, issued December 27, 1955; and Leubner and Murray U.S. Patent 2,728,665, issued December 27, 1955; the triazoles of Heimbach and Kelly U.S. Patent 2,444,608, issued July 6, 1948; the azaindenes of Heimbach and Kelly U.S. Patents 2,444,605 and 2,444,- 606, issued July 6, 1948; Heirnbach U.S. Patents 2,444,- 607, issued July 6, 1948, and 2,450,397, issued September 28, 1948; l-ieimbach and Clark U.S.
  • Patent 2,444,609 issued July 6, 1958; Allen and Reynolds U.S. Patents 2,713; 541, issued July 19, 1955, and 2,743,181, issued April 24, 1956; Carroll and Beach U.S. Patent 2,716,062, issued August 23, 1955; Allen and Beilfuss U.S. Patent 2,735,- 769, issued February 21, 1956; Reynolds and Sagal U.S. Patent 2,756,147, issued July 24, 1956; Allen and Sagura U.S. Patent 2,772,164, issued November 27, 1956, and those disclosed by Birr in Z. wiss. Phot, vol.
  • the emulsions may also contain speed-increasing compounds of the quaternary ammonium type of Carroll U.S. Patent 2,271,623, issued February 3, 1942; Carroll and Allen U.S. Patent 2,288,226, issued June 30, 1942; and Carroll and Spence U.S. Patent 2,334,864, issued November 23, 1943; and the polyethyleneglycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10, 1955.
  • the emulsions may contain a suitable gelatin plasticizer such as glycerin; a dihydroxy alkane such as 1,5-pentane diol as described in Milton and Murry U.S. application Serial No. 588,951, filed June 4, 1956; an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate) as described in Milton U.S. application Serial No. 662,564, filed May 31, 1957; bis-(ethoxy diethylene glycol) succinate as described in Gray U.S. application Serial No.
  • the emulsions may be hardened with any suitable hardener for gelatin such as formaldehyde; a halogen-substituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937; a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo (2,2,2)-7-octene-2,3,5,6-tetracarboxylic dianhydride, or a dicarboxylic or a disulfonic acid chloride such as terephthaloyl chloride or naphthalene-1,5-disulfonyl chloride as described in Allen and Carroll U.S.
  • any suitable hardener for gelatin such as formaldehyde
  • a halogen-substituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937
  • Patent 2,732,316 issued January 24, 1956; a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 2-3 carbon atoms, such as ,B-methyl glutaraldehyde bis-sodium bisulfite as described in Allen and Burness U.S. Patent application Serial No. 556,031, filed December 29, 1955; a bis-aziridine carboxamide such as trimethylene bis(1- aziridine carboxamide) as described in Allen and Webster U.S. Patent application Serial No. 599,891, filed July 25, 1956; or 2,3-dihydroxy dioxane as described in Jeifreys U.S. Patent 2,870,013, issued January 20, 1957.
  • the emulsions may contain a coating aid such as saponin; a lauryl or oleyl monoether oi polyethyleneglycol as described in Knox and Davis U.S. Patent 2,831,766, issued April 22, 1958; a salt of a sulfated and alkylated polyethyleneglycol ether as described in Knox and Davis U.S. Patent 2,719,087, issued September 27, 1955; an acylated alkyl taurine such as the sodium salt of N-oleoyl-N-methyl taurine as described in Knox, Twardokus and Davis U.S.
  • a coating aid such as saponin
  • a lauryl or oleyl monoether oi polyethyleneglycol as described in Knox and Davis U.S. Patent 2,831,766, issued April 22, 1958
  • a salt of a sulfated and alkylated polyethyleneglycol ether as described in Knox and Davis U.S. Patent 2,719,087, issued September 27, 1955
  • Patent 2,739,891 issued March 27, 1956; the reaction product of a dianhydride of tetracarboxybutane with an alcohol or an aliphatic amine containing from 8 to 18 carbon atoms which is treated with a base, for example, the sodium salt of the monoester of tetracarboxybutane as described in Knox, Stenberg and Wilson U.S. Patent 2,843,487, issued July 15, 1958; a water-soluble maleopimarate or a mixture of a Water-soluble maleopimarate and a substituted glutamate salt as described in Knox and Fowler U.S.
  • Patent 2,823,123 issued February 11, 1958; an alkali metal salt of a substituted amino acid such as disodium N-(carbop-tert. octylphenoxypentaethoxy)-glutamate as described in Knox and Wilson U.S. patent application Serial No. 600,679, filed July 30, 1956; or a sulfosuccinamate such as tetrasodium N-(l,2-dicarboxyethyl)- N-octadecyl sulfosuccinamate or N-lauryl disodium sulfosuccinamate as described in Knox and Stenberg U.S. patent application Serial No. 691,125, filed October 21, 1957.
  • 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 U.S. 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 U.S.
  • Patent 2,768,154 issued October 23, 1956; or containing cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest U.S. Patent 2,808,331, issued October 1, 1957; 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 U.S. Patent 2,852,382, of lllingsworth, Dann and Gates, issued September 16, 1958.
  • cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest U.S. Patent 2,808,331, issued October 1, 1957; 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 U.S. Patent 2,852,382, of lllingsworth, Dann and Gates, issued September 16, 1958.
  • 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 Lowry Red (Wratten No. 92) filter referred to above transmits only radiation beyond about 630 m (i.e., absorbs substantially all radiation less. than about 630 Inn).
  • a photographic reversal color process for processing a photoexposed multi-layer photographic element comprising a support and a photographic silver halide emulsion sensitive to the blue region of the spectrum, a photographic silver halide emulsion spectrally sensitized to the green region of the spectrum and a photographic silver halide emulsion spectrally sensitized to the red region of the spectrum, comprising developing said photographic element in a photographic developer for producing at least one black-and-white negative image but no color image, subjecting said photographic element to at least one reversal re-exposure, contacting the silver halide emulsion layers of said photographic element with an aqueous solution consisting essentially of water and at least 0.25 gram per liter of a compound selected from the class represented by the following general formula:
  • R represents a member selected from the class consisting of a hydrogen atom and a lower alkyl group
  • R represents a member selected from the class consisting of a hydrogen atom, an aryl group and an arylenethiazolyl group
  • D represents the non-metallic atoms necessary to complete an aromatic nucleus
  • X represents an acid radical
  • n represents a positive integer of from 1 to 26 when R represents a member selected from the class consisting of a hydrogen atom and an arylenethiazolyl group
  • n represents a positive integer of from 1 to 3 when R represents an aryl group
  • a photographic reversal color process for processing a photoexposed multi-layer photographic element comprising a support and at least one photographic silver halide emulsion layer sensitive to the blue region of the spectrum, at least one photographic silver halide emulsion spectrally sensitized to the green region of the spectrum and at least one photographic silver halide emulsion spectrally sensitized to the red region of the spectrum, comprising developing said photographic element in a photographic developer for producing only a black-andwhite negative image, contacting said silver halide emulsion layers with an aqueous solution consisting essentially of water and at least 0.25 gram per liter of a compound selected -from the class represented by the following general formula:
  • R represents a member selected from the class consisting of a hydrogen atom and an arylenethiazolyl group
  • n represents a positive integer of from 1 to 3 when R represents an aryl group
  • a photographic reversal color process for processing a photoexposed multi-layer photographic element comprising a photographic silver halide emulsion sensitive to the blue region of the spectrum, a photographic silver halide emulsion spectrally sensitized to the green region of the spectrum and a photographic silver halide emulsion spectrally sensitized to the red region of the spectrum, comprising subjecting said photo-graphic element to development in a photographic developer for producing only a black-and-white negative image, followed by separate reversal re-eXpo-sure and color development for each of said emulsions in a photographic color developer containing a color forming compound capable of coupling with the oxidation products of said photographic color developer to produce a colored image complementary to the region of the spectrum to which each of said photographic silver halide emulsions is sensitive, the photographic silver halide emulsions of said photographic element being treated after negative development but before any color development with an aqueous solution consisting essentially of water and at least 0.25
  • R represents a member selected from the class consisting of a hydrogen atom and a lower alkyl group
  • R represents a member selected from the class consisting of a hydrogen atom, an aryl group and an arylenethiazolyl group
  • D represents the non-metallic atoms necessary to complete an aromatic nucleus
  • X represents an acid radical
  • n represents a positive integer of from 1 to 26 when R represents a member selected from the class consisting of a hydrogen atom and an arylenethiazolyl group
  • n represents a positive integer of from 1 to 3 when R represents an aryl group.
  • a photographic reversal color process for processing a photoexposed multi-layer photographic element comprising a photographic silver halide emulsion sensitive to the blue region of the spectrum, a photographic silver halide emulsion spectrally sensitized to the green region of the spectrum and a photographic silver halide emulsion spectrally sensitized to the red region of the spectrum, comprising subjecting said photographic element to development in a photographic developer for producing only a blacl -and-white negative image, followed by separate reversal re-exposure and color development for each of said emulsions in a photographic color developer containing a color forming compound capable of coupling with the oxidation products of said photographic color developer to produce a colored image complementary to the region of the spectrum to which each of said photographic silver halide emulsions is sensitive, the photographic silver halide emulsions of said photographic element being treated after negative development but betime any color development with an aqueous solution consisting essentially of water and at least 025
  • R represents a member selected from the class consisting of a hydrogen atom and a lower alkyl group
  • R represents an aryl group
  • D represents the non-metallic atoms necessary to complete an aromatic nucleus
  • X represents an acid radical
  • n represents a positive integer of from 1 to 3.
  • a photographic reversal color process for processing a photoexposed multi-layer photographic element comprising a photographic silver halide emulsion sensitive to the blue region of the spectrum, a photographic silver halide emulsion spectrally sensitized to the green region of the spectrum and a photographic silver halide emulsion spectrally sensitized to the red region of the spectrum, comprising subjecting said photographic element to development in a photographic developer for producing only a black-and-white negative image, followed by separate reversal re-eXposure and color development for each of said emulsions in a photographic color developer containing a color-forming compound capable of coupling with the oxidation products of said photographic color developer to produce a colored image complementary to the region of the spectrum to which wherein R represents a member selected from the class consisting of a hydrogen atom and a lower alkyl group, R represents a hydrogen atom, D represents the nonmetallic atoms necessary to complete an aromatic nucleus, X represents an acid radical and n
  • a photographic reversal color process for processing a photoexposed multi-layer photographic element comprising a photographic silver halide emulsion sensitive to the blue region of the spectrum, a photographic silver halide emulsion spectrally sensitized to the green region of the spectrum and a photographic silver halide emulsion spectrally sensitized to the red region of the spectrum, comprising subjecting said photographic element to development in a photographic developer for producing only a black-and-white negative image, following by separate reversal re-exposure and color development for each of said emulsions in a photographic color developer containing a color-forming compound capable of coupling 'with the oxidation products of said photographic color developer to produce a colored image complementary to the region of the spectrum to which each of said photographic silver halide emulsions is sensitive, the photographic silver halide emulsions of said photographic element being treated after negative development but before any color development with an aqueous solution consisting essentially of water and at least 0.25 gram per
  • R represents a member selected from the class consisting of a hydrogen atom and a lower alkyl group, 1) represents the non-metallic atoms necessary to complete an aromatic nucleus, X represents an acid radical, and m represents a positive integer of from 1 to 26.
  • a photographic reversal color process for processing a photoexposed multi-layer photographic element comprising a photographic silver halide emulsion substantially sensitive only to the blue region of the visible spectrum, a photographic silver halide emulsion spectrally sensitized to the green region of the visible spectrum and a photographic silver halide emulsion spectrally sensitized to the red region of the visible spectrum, comprising subjecting said photographic element to development in a photographic developer for producing only a black-and- White negative image, exposing the red sensitive emulsion of said photographic element to red radiation, developing said red sensitive silver halide emulsion in a color developer containing a col-or forming compound capable of coupling with the oxidation products of the color developing agent of said photographic color developer to produce a cyan image, the photographic silver halide emulsion spectrally sensitized to the red region of the visible spectrum being treated after negative develop- 16 ment but before any color development with an aqueous solution consisting essentially of Water and at least 0.
  • R represents a member selected from the class consisting of a hydrogen atom and a lower alkyl group
  • R represents an aryl group
  • D represents the non-metallic atoms necessary to complete an aromatic nucleus
  • X represents an acid radical
  • n represents a positive integer of from 1 to 3
  • said photographic element being washed with water after treatment in said aqueous solution, and after production of said cyan image in said red-sensitized silver halide emulsion layer, exposing said blue sensitive silver halide emulsion layer to blue light and developing said blue sensitive silver halide emulsion in a photographic color developer for producing a yellow image in said blue sensitive silver halide emulsion layer, fogging the unexposed silver halide in said green-sensitized silver halide emulsion layer and developing said green-sensitized silver halide emulsion layer in a photographic color developer for producing a magenta image, the color-forming compounds for producing the respective yellow and mag
  • a photographic reversal color process for processing a photoexposed multi-layer photographic element comprising a photographic silver halide emulsion substantially sensitive only to the blue region of the visible spectrum, a photographic silver halide emulsion spectrally sensitized to the green region of the visible spectrum and a photographic silver halide emulsion spectrally sensitized to the red region of the visible spectrum, comprising subjecting said photographic element to development in a photographic developer for producing only a black-andlwhite negative image, exposing the red sensitive emulsion of said photographic element to red radiation, developing said red sensitive silver halide emulsion in a color developer containing a color-forming compound capable of coupling with the oxidation products of the color developing agent of said photographic color developer to produce a cyan image, the photographic silver halide emulsion spectrally sensitized to the red region of the visible spectrum being treated after negative development but before any color development with an aqueous solution consistiong essentially of water and at least 0.25 gram per
  • R represents a member selected from the class consisting of a hydrogen atom and a lower alkyl group
  • R represents a hydrogen atom
  • D represents the nonrnetallic atoms necessary to complete an aromatic nucleus
  • X represents an acid radical
  • n represents a positive integer of from 1 to 26
  • said photographic element being washed with water after treatment in said aqueous solution, and after production of said cyan image :in said redsensitized silver halide emulsion layer, exposing said blue sensitive silver halide emulsion layer to blue light and developing said blue sensitive silver halide emulsion in a photographic color developer for producing a yellow image in said blue sensitive silver halide emulsion layer, fogging the unexposed silver halide in said green-sensitized silver halide emulsion layer and developing said green sensitized silver halide emulsion layer in a photographic color developer for producing a magenta image, the colorforrning compounds for producing the respective yellow and
  • a photographic reversal color process for processing a photoex-posed multi-layer photographic element comprising a photographic silver halide emulsion substantially sensitive only to the blue region of the visible spectrum, a photographic silver halide emulsion spectrally sensitized to the green region of the visible spectrum and a photographic silver halide emulsion spectrally sensitized to the red region of the visible spectrum, comprising subjecting said photographic element to development in a photographic developer for producing only a black-andwhite negative image, exposing the red sensitive emulsion of said photographic element to red radiation, developing said red sensitive silver halide emulsion in a color developer containing a color-forming compound capable of coupling with the oxidation products of the color developing agent of said photographic color developer to produce a cyan image, the photographic silver halide emulsion spectrally sensitized to the red region of the visible spectrum being treated after negative develop ment but before any color development with an aqueous solution consisting essentially of water and at least 0.25 gram per

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  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
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US819539A 1959-06-11 1959-06-11 Reducing fog in reversal color films processed in developers containing couplers Expired - Lifetime US3113864A (en)

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US819539A US3113864A (en) 1959-06-11 1959-06-11 Reducing fog in reversal color films processed in developers containing couplers
GB20160/60A GB952339A (en) 1959-06-11 1960-06-08 Improvements in photographic colour processing
FR829481A FR1264116A (fr) 1959-06-11 1960-06-09 Nouveau procédé de traitement de films en couleurs

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3168400A (en) * 1961-05-22 1965-02-02 Eastman Kodak Co Rapid processing of photographic color materials
US3206310A (en) * 1961-08-25 1965-09-14 Eastman Kodak Co Modification of colloidal metals and metal sulfides to reduce action as a nucleus for physical development
US3342596A (en) * 1964-03-11 1967-09-19 Eastman Kodak Co Benzothiazolium compounds for controlling overdevelopment
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US20060244163A1 (en) * 2002-12-12 2006-11-02 Koji Matsumoto Method for producing polarizing film
WO2012035314A1 (en) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Photographic paper
WO2021213762A1 (en) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Photographic paper

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2356486A (en) * 1943-04-15 1944-08-22 Eastman Kodak Co Stain prevention in color photography
US2376141A (en) * 1941-12-29 1945-05-15 Eastman Kodak Co Fine grain developers
US2384663A (en) * 1943-08-21 1945-09-11 Eastman Kodak Co Method of preventing aerial oxidation and color stain
US2648604A (en) * 1951-12-28 1953-08-11 Gen Aniline & Film Corp Photographic developer containing a pyridinium salt and process of development
US2694716A (en) * 1951-10-17 1954-11-16 Eastman Kodak Co Polymethylene-bis-benzothiazolium salts
US2899306A (en) * 1957-01-24 1959-08-11 Yh hci

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2376141A (en) * 1941-12-29 1945-05-15 Eastman Kodak Co Fine grain developers
US2356486A (en) * 1943-04-15 1944-08-22 Eastman Kodak Co Stain prevention in color photography
US2384663A (en) * 1943-08-21 1945-09-11 Eastman Kodak Co Method of preventing aerial oxidation and color stain
US2694716A (en) * 1951-10-17 1954-11-16 Eastman Kodak Co Polymethylene-bis-benzothiazolium salts
US2648604A (en) * 1951-12-28 1953-08-11 Gen Aniline & Film Corp Photographic developer containing a pyridinium salt and process of development
US2899306A (en) * 1957-01-24 1959-08-11 Yh hci

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3168400A (en) * 1961-05-22 1965-02-02 Eastman Kodak Co Rapid processing of photographic color materials
US3206310A (en) * 1961-08-25 1965-09-14 Eastman Kodak Co Modification of colloidal metals and metal sulfides to reduce action as a nucleus for physical development
US3342596A (en) * 1964-03-11 1967-09-19 Eastman Kodak Co Benzothiazolium compounds for controlling overdevelopment
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US20060244163A1 (en) * 2002-12-12 2006-11-02 Koji Matsumoto Method for producing polarizing film
US8012383B2 (en) * 2002-12-12 2011-09-06 Sumitomo Chemical Company, Limited Method for producing polarizing film
WO2012035314A1 (en) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Photographic paper
WO2021213762A1 (en) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Photographic paper

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BE591664A (sh)

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