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
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/407—Development processes or agents therefor
  • G03C7/413—Developers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/145—Infrared
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/167—X-ray

Definitions

• This invention relates to color photography, and more particularly, to a method of processing multi-layer color films or papers by the technique of reversal color development.
• multi-layer photographic elements used for color photography there are generally three selectively sensitive emulsion layers (each of which may consist of several strata finished to different speed levels) coated on the same side of a photographic support, such as film or paper.
• a photographic support such as film or paper.
• the uppermost layer is frequently a blue-sensitive layer
• the next light-sensitive layer is generally green-sensitive
• the light-sensitive layer closest to the support is generally sensitized to the red region of the spectrum.
• photographic elements inasmuch as many photographic silver halide emulsions have substantial inherent sensitivity in the blue spectral region, such photographic elements generally have a yellow filter layer coated beneath the blue-sensitive outermost layer for the purpose of absorbing substantially all blue radiation which would otherwise be transmitted to the green-sensitized and redsensitized layers.
• Such multi-layer photographic elements can also have other layers for specialized purposes including light sensitive emulsion layers, gelatin or other subbing layers, antihalation layers, etc.
• Typical multilayer photographic materials useful in our invention have been described in the prior art, such as Mannes et al. US. Patent 2,252,718, issued August 19, 1951.
• Color materials of the type advantageously employed in the present invention are those intended primarily for reversal color processes, in which the photoexposed material is given a conventional black-and-white development to produce a negative silver image but no color image, followed by at least one reversal re-exposure and color development to produce positive dye (and silver) images.
• the color materials used in our invention comprise those which contain the color-forming materials or couplers within the silver halide emulsions, or those materials designed for processing in developers which contain the color couplers or color-forming compounds within the color developer. The latter materials are particularly useful in practicing the present invention for reasons pointed out below.
• an object of our invention to provide an improved process for producing photographic images in color by reversal color photography. Another object is to provide improved developers for such reversal color photographic processes. Still another object is to provide a method of increasing the color density in certain of the emulsion layers of photographic color elements, particularly in the red-sensitive of cyan-producing layer. Still another object is to provide a convenient means for avoiding re-eXposure by light, by simultaneously fogging and color developing photographic silver halide emulsion to produce a colored image of high maximum density. Other objects will become apparent from a consideration of the following description and examples.
• the conventional procedure is to selectively re-expose with colored light (or chemicals) each of the selectively sensitized layers and to separately develop each of these layers to a colored image in a color developer which contains the appropriate color-forming ingredient in the color developer.
• color processes of this type it is frequently desired to accelerate color development so that the rate of development is increased without fogging the silver halide grains which have not been exposed by the selective exposure.
• Such accelerators increase the maximum color density with little or no increase in color fog.
• the compounds of our invention can be used to increase the development rate of multi-layer photographic materials which are processed in developing solutions containing the color-forming components in the color developing solutions so that substantially all silver halide, which has been selectively re-exposed to a particular region of the spectrum, becomes developed in the subsequent color developing solution, thus preventing the formation of undesirable color fog as a consquence of further color development in a subsequent color developer for producing different colored images.
• thioether compounds useful in practicing our invention by incorporation in the color developer comprise compounds represented by the following general formula:
• X represents a divalent linkage, such as oxygen, sulfur,
• R represents a hydroxyl group, an allcoxyl group (e.g.,' methoxyl, ethoxyl, propoxyl, butoxyl, etc), a carbamyl group (i.e., an aminocarbonyl group), or a carboxylic acyloxyl group, such as acetoxyl, bntyroxyl, etc.
• R represents an ethylene radical, such as ethylene or ethylene Cs substituted by an alkyl radical, such as methyl, ethyl, etc, represents a positive integer of from 1 to 2 and n represents a positive integer of from 1 to 3.
• R and R each represents an 'alky'lene group, such as ethylene, trimethylene, tetramethylene (butylene), methyl-substituted trimethylene, pentamethylene, ethyl-substituted tetramethylene, hexamethylene, 'heptamethylene, octa'methylene, nonamethylene, decamethylene, et-c. (e.g., a hydrocarbon alkylene group containing from about 2 to 11) carbon atoms), and d represents a positive integer of from 1 to 3.
• dithiaalkylencd-iols such as those embraced by the following general formula:
• n each represents a positive integer of from about 2 to 10.
• the concentration of the thioether compound in the color developer is at least 0.1 gram per liter. Larger amounts of-thioether compounds can be employed in the color developers, and concentrations as high as 5 grams (or higher) per liter are useful.
• the activity of the color developers will obviously depend upon the development temperature, duration of development and the like. All of these variables are Well understood by those skilled in the art of photography.
• the most advantageous concentration for a particular developer can be determined by developing a series of test strips of silver halide emulsions wherein the concentration of thioether compound is varied.
• the color developers useful in our invention can also contain conventional addenda, such as alkaline salts (e.g., sodium carbonate, potassium carbonate, sodium hydroxide, sodium, metaborate, etc.), restraining agents, such as potassium bromide, stain preventives, such as alkali metal sulfites, etc. i
• photographic emulsions used in practicing our invention are of the developing-out type.
• 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. Patent 1,574,944, issued March 2, 1926, Sheppard et al. US. Patent 1,623,499, issued April 5, 1927, and Sheppard et al. US. 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.
• the noble metals such as ruthenium, rhodium, palladium, iridium, and platinum.
• Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and
• sodium chloropall'adite 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 antifoggants in higher amounts, as described in Trivelli and Smith US. 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. US. Patent 2,399,- 083, issued April 23, 1946, and Damschroder et al. US. Patent 2,642,361, issued June 16, 1953.
• Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2- 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 diethylene triamine (Lowe and Jones US. 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(fl-amiuoethyl) sulfide and its Water-soluble salts (Lowe and Jones US. 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 diethylene triamine (Lowe and Jones US. 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(fl-amiuoethyl) s
• the emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker US. Patents 1,846,301, issued February 23, 1932; 1,846,302, issued February 23, 1932; and 1,942,854, issued January 9, 1934; White US. Patent 1,990,507, issued February 12, 1935; Brooker and White US. 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 US. Patent 2,493,748, issued January 10, 1950; Sprague US.
• cyanine and merocyanine dyes such as those described in Brooker US. Patents 1,846,301, issued February 23, 1932; 1,846,302, issued February 23, 1932; and 1,942,854, issued January 9, 1934; White US. Patent 1,990,507, issued February 12, 1935; Brooker and White US. Patents 2,112,140, issued March 22, 1938; 2,165
• 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 US. Patent 2,728,664, issued December 27, 1955; and Leubner and Murray US. Patent 2,728,665, issued December 27, 1955; or with gold salts as described in Damschroder US. Patent 2,597,856, issued May 27, 1952,
• the emulsions may also contain speed increasing com- 7 pounds 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; or the polyethylene. glycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10,195; or the quaternary ammonium salts and polyethylene glycols of Piper U.S. Patent 2,886,437, issued May 12,
• T he emulsions may contain .a suitable gelatin plasticizer such as glycerin; a dihydroxy alkane such as 1,5-pentane diol as described in Milton and Murray U.S. application Serial No. 588,951, filed June 4, 1956 (now U.S. Patent 2,960,404, issued November 15, 1960); an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate) as described in Milton U.S. Patent 2,904,434, issued September 15, 1959; bis-(ethoxy diethylene glycol) succinate as described in Gray U.S. application Serial No. 604,333, filed August 16, 1956 (now U.S.
• the plasticizer may be added to the emulsion before or after the addition of a sensitizing dye, if used.
• 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-tetra-carboxylic dianhydride, or a dica'rboxylic or adisulfonic acid chloride such as terephthaloylchloride 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
• a compound having a plurality of acid anhydride groups such as 7,8-diphen
• Patent 2,950,197 issued August 23, 1960
• 2,3-dihydroxy dioxane as described in JelTreys
• bisisocyanate as described in Henn et a1.
• the emulsions may contain a coating aid such as saponin; a 'lauryl or oleyl monoether of polyethylene glycol as described in Knox and Davis U.S. Patent 2,831,766, issued April 22, 1958; a salt of a sultated and alkylated polyethylene glycol 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 of polyethylene glycol as described in Knox and Davis U.S. Patent 2,831,766, issued April 22, 1958
• a salt of a sultated and alkylated polyethylene glycol 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 tetracar-- boxybutane 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 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-(carbo p tert.
• 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 as described in Knox and Fowler U.S. Patent 2,823,123, issued February
• the addenda which we have described may be used in various kinds of photographic emulsions. In addition to being useful in X-ray and other nonoptically sensitized emulsions they may also be used in orthochromatic, panchromatic, and infrared sensitive emulsions. They may be added to the emulsion before or after any sensitizing dyes which are used.
• Various silver salts may be used as the sensitive salt such assilver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide.
• the agents maybe used in emulsions intended for color photography, for example, emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other color-generating materials, emulsions of the mixed-packet type, such as described in Godowsky U.S. Patent 2,698,794, issued January 4, 1955; or emulsions of the mixed-grain type, such as described in Carroll and Hanson U.S. Patent 2,592,243, issued April 8, 1952.
• These agents can also be used in emulsions which form latent images predominantly on the surface of the silver halide crystal or in emulsions which form latent images predominantly inside the silver halide crystal, such as those described in Davey and Knott U.S. Patent 2,592,250, issued Apr-i1 8; 1952.
• 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 poyvinyl compound.
• colloidal albumin a colloidal albumin
• a cellulose derivative a synthetic resin
• poyvinyl compound a colloidal compound 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,
• 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 US. Patent 2,888,331, 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 Us. Patent 2,852,382, of Illingsworth, 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.
• Couplers or color-forming compounds which are soluble in the strongly alkaline developing solutions are well known to those skilled in the art.
• Typical couplers include the following:
• amylbenzenesulfonylamino) -5- pyrazolone (37) 1-phenyl-3-[p-(p-sec. amylbenzoyl) aminobenzoylamino]-5-pyrazolone (3 8) 1-m-tolyl-3-[m-(fi-phenylpropionyl) aminobenzoylamino] -5-pyrazolone (39) 1-m-tolyl-3-(2,4-di-tert.butyl-mtolyloxyacetylamino) -5-pyrazolone (40) 1-[p'-(p-tert.
• amylphenoxyacetanilide (77) benzoylacetamido-3-methoxy-2,4'-di-tert.-
• Couplers suitable for use in the emulsions of our invention comprise those disclosed in Spence and Carroll US. Patent 2,640,776, issued June 2, 1953, Weissberger et al. US. Patent 2,407,210, issued September 3, 1946, and Weissberger et al. US. Patent 2,474,293,
• the color-forming developers useful in our invention have been previously described in the prior art, and our invention is not to be restricted to the use of any particular color-forming developer.
• the color-forming developers previously mentioned which we have found to be especially useful in our invention. comprise aromatic primary 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 excellent results when employed in combination with the formamidinothiomethyl compounds of our invention.
• Typical of such color-forming developers are the sulfonamido substituted p-phenylenediamines disclosed in Weissberger US. Patent 2,548,574, issued April 10,
• the first developer employed in the process of our invention is generally a rapid developer of the MO type
• filter i.e., a filter transmitting only visible radiation beyond about 620 III/.1. with maximum transmittance of about 88 percent at 700 mu.
• Each of the strips was developed for ten minutes at 80 F. in a cyan developer having the composition given below.
• One of the film strips served as a control and contained no thioether compound, while the other strips were developed in cyan developers containing thioether compounds in amounts identified in the following table.
• the compound numbers in the table correspond to the compound numbers given above for the thioether compounds.
• the cyan developer which served as a control and to which the thioether compounds were added had the following formula:
• a multi-layer color film of the type used in Example 1 was cut into several strips and each of these exposed for second to a SOD-watt 3000 K. light source on an Eastman Type Ib Sensitometer. Each of the strips was then developed for nine minutes at 80 F. to a black-andwhite negative developer of the type described in the above example and washed for five minutes in 80 F. water. Strips were then treated in an antifoggant bath of the type described in the above example for two minutes at 80 F. and washed for two minutes in 80 F.
• R represents a member selected from the class consisting of a hydroxyl group, an alkoxyl group, and a carbamyl group
• R represents an ethylene radical
• X represents a divalent radical selected from the class consisting of an oxygen atom, a sulfur atom and the group X CH CH X X and X each represents a divalent radical selected from, the class consisting of an oxygen atom and a sulfur atom, provided at least one of the radicals selected from the class consisting of X, X and X represents a sulfur atom
• X represents the divalent radical d represents a positive whole number of from 1 to 2 and n represents a positive whole number of from 1 to 3.
• a photographic color developer comprising an aquous alkaline solution of a p-phenylenediamine color developing agent, a color-forming compound capable of coupling with the oxidation products of said color developing agent to provide a colored image, and a non-pol l V ymeric compound selected from those represented by the following general formula:
• R represents a member selected from the class consisting of a hydroxyl group, an alkoxyl group, and a carbamyl group
• R represents an ethylene radical
• X represents a divalent radical selected from the class consisting of an oxygen atom, a sulfur atom
• X CH CH X1, X and X each represents a divalent radical selected from the class consisting of an oxygen atom and a sulfur atom, provided at least one of the radicals selected from the class consistmg of X, X and X represents a sulfur atom, X represents the divalent radical wherein R represents a member selected from the class consisting of a hydroxyl group, an alkoxyl group and a carbamyl group, X represents a divalent radical selected from the class consisting of an oxygen atom, a sulfur atom,
• a photographic color developer comprising an aqueous alkaline solution, of a p-phenylenediamine color developing agent, a phenolic compound capable of coupling with the oxidation products of said color developing agent to provide a cyan photographic image, and a nonpolymeric compound selected from those represented by the following general formula:
• R represents a member selected from the class consisting of a hydroxyl group, an :alkoxyl group, and a caroamyl group
• R represents an ethylene radical
• X represents a divalent radical selected from the class con- 'sisting of an oxygen atom, a sulfur atom
• NHCI-I2NHC- and the radical X CH CH X X and X each represents a divalent radical selected from the class consisting of an oxygen atom and a sulfur atom, provided at least one of the radicals selected from the class consisting of X, X and X represents a sulfur atom, and n represents a positive whole number of from 1 to 3.
• a photographic color developer comprising an aqueous alkalinesolution of a p-phenylenediamine color developing agent, a compound capable of coupling with the oxidation products of said color developing agent to produce a colored photographic image, and a non-polymeric compound selected from those represented by the following general formula:
• R and R each represents a hydrocarbon alkylene group containing from about 2 to 10 carbon atoms and d represents a positive integer of from 1 to 3.
• a photographic color developer comprising an aqueous alkaline solution of a p-phenylenediamine color de veloping agent, a compound capable of coupling with'the oxidation products of said color developing agent to produce a colored photographic image, and a non-polymeric compound selected from those represented by the following general formulai wherein m and it each represents a positive integer of from about 2 to 10.
• a photographic color developer comprising an aqueous alkaline solution of a p-phenylenediamine color developing agent, a pyrazolone compound capable of coupling with the oxidation products of said color developing agent to produce a magenta photographic image and a non-polymeric sompound selected from those represented by the following general formula:
• R and R each represents a hydrocarbon alkylene group containing from about 2 to 10 carbon atoms and d represents a positive integer of from 1 to 3.
• a photographic color developer comprising an aqueous alkaline solution of an arylenediamine color developer and the compound having the formula:
• a photographic color developer comprising an aqueous alkaline solution of an arylenediamine color developer and the compound having the formula:
• a photographic color developer comprising an aqueous alkaline solution of an arylenediamine color developer and'the compound having'the formula:
• a photographic color developer comprising an aqueous alkaline solution of an arylenediamine color deveioper and the compound having the formula:
• a photographic color developer comprising an aqueous alkaline solution of an arylenediamine color de veloper and the compound having the formula:

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• Physics & Mathematics (AREA)
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• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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  • BE BE622218D patent/BE622218A/xx unknown
• 1961
  • 1961-09-11 US US137041A patent/US3201242A/en not_active Expired - Lifetime
• 1962
  • 1962-09-01 DE DEE23468A patent/DE1147845B/de active Pending
  • 1962-09-07 GB GB22017/65A patent/GB1020033A/en not_active Expired
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