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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
  • G03C8/045—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals with the formation of a subtractive dye image
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/261—Non-bath processes, e.g. using pastes, webs, viscous compositions

Definitions

• Photographic color elements having a support coated on one side with at least one light-sensitive hydrophilic colloid layer containing imagewise-exposed silver halide grains and a nondiffusible coupler that reacts with oxidized aromatic primary amine color developing agent to form a nondilfusible dye, are advantageously processed by (l) contacting with a hydrophilic colloid processing web containing silver precipitating nuclei, an aromatic primary amine color developing agent, an organic amine-S0 addition product and, alternatively, an additional silver halide solvent until a dye image and silver image are formed in the element and a silver image is formed in the processing web, (2) separating the processing web from the element and, if desired, subsequently treating the element to remove silver and residual silver halide, provided that the hydrophilic colloid in the element and the hydrophilic colloid in the processing web are either hardened during manufacture or during step (1) by a hardener imbibed in the processing web just prior to step 1) to have
• This invention is related to photography and more particularly to color photographic processing.
• an exposed emulsion layer is developed in the presence of a silver halide solvent, the emulsion layer being for at least a portion, or for the whole of the development period, in effective contact with a receiving sheet, the surface of which generally carries a quantity of a silver precipitant which comprises either physical development nuclei such as colloidal silver or silver sulfide or a chemical precipitant for silver ions, such as zinc sulfide.
• Development of the emulsion layer proceeds accompanied by complexing of the residual unexposed and undeveloped silver halide with a silver halide solvent also present in the developer composition, and imagewise diffusion of the resulting silver complex to the receiving sheet where the silver precipitant causes the formation of an argental image.
• Another object of this invention is the provision of a novel process for a color film that is essentially free of excess liquid in the color development step.
• the photographic element comprises a support coated with at least one hydrophilic colloid layer containing dispersed silver halide grains [preferably camera speed (e.g., ASA speed of from 5 to 5000) silver bromoiodide grains] and a nonditfusible dye-forming coupler that reacts with an oxidized aromatic primary amine color developing agent to produce a nondiftusible dye.
• the hydrophilic colloid processing web and hydrophilic colloid emulsion layers are either hardened during manufacture or during the web processing step by a hardening agent imbibed in the processing web so they each have a reticulation temperature greater than 65 C.
• a melting point greater than C. determined by observing the hydrophilic colloid layer on a sample strip immersed in a mechanically stirred distilled water bath at 23 C. as it is heated to give a 3.3 C. temperature rise per minute up to C. (maintained for 2 minutes), the reticulation temperature being the bath temperature at which the layer shows the first sign of reticulation and the melting point being the bath temperature at which the layer shows the first evdience of stripping, sloughing off or frilling (in areas 15 mm. from the edge of sample).
• Our process comprises the steps:
• the hydrophilic colloid processing web which contains silver precipitating agent, an alkali, an aromatic primary amine color developing agent and a silver halide solvent until substantially all of the developable silver halide grains (i.e., exposed grains in color negative emulsions or unexposed grains in color directpositive emulsions) in the photographic element are developed to a silver and a nondiffusible dye image, and at least a part of the residual undeveloped silver halide grains in areas not color developed in the photographic element are dissolved by the silver halide solvent and transferred imagewise to the hydrophilic colloid processing web Where a silver image is formed on the silver precipitating agent, the processing web containing a sutficient amount of a hardening agent to harden both web and hydrophilic colloid layers of the element when these layers are not hardened during manufacture; and
• step (2) is continued to remove the silver image and any residual silver halide so that the dye image is unobstructed and made permanent by following step (2) with steps (3) and (4) or alternatively step (5) is used in place of steps (3) and (4).
• a silver bleach bath comprising a photographic silver oxidizing agent (e.g., an alkali metal ferricyanide, an alkali metal dichromate, quinone, etc.) until the silver is converted to a silver salt; and
• a photographic silver oxidizing agent e.g., an alkali metal ferricyanide, an alkali metal dichromate, quinone, etc.
• a photographic fixing bath comprising a silver salt solvent (e.g., an alkali metal or ammonium thiosulfate, an alkali metal or ammonium thiocyanate, thiourea, etc.) until the silver salt(s) is dissolved and diffuses from the photographic element;
• a silver salt solvent e.g., an alkali metal or ammonium thiosulfate, an alkali metal or ammonium thiocyanate, thiourea, etc.
• a combined bleach-and-fix solution comprising a silver oxidizing agent [e.g., an alkali metal ferricyanide, a
• salt with an unchelated cation e.g., alkali metal or ammonium
• an anion that is Fe+++, Co+++ or Cu++ chelated with a polyfunctional ligand e.g., a polycarboxylic or polyphosphoric acid chelating agent
• a polyfunctional ligand e.g., a polycarboxylic or polyphosphoric acid chelating agent
• a silver salt solvent e.g., an alkali metal or ammonium thiosulfate, an alkali metal or ammonium thiocyanate, etc. until the silver and silver salt(s) is dissolved and diffuses from the photographic element.
• the hydrophilic colloid processing web used in step (1) contains dispersed silver precipitating agent, and at the time of contact with the image-exposed photographic element, sufficient processing solution to develop substantially all the developable silver halide, and to simultaneously form a color dye image in emulsion layer(s) of the photographic element.
• the processing solution contains an aromatic primary amine color developing agent, an organic amine -SO addition product and, option ally, additional silver halide solvent and where necessary a hardening agent.
• the processing solution also advantageously contains a suitable toning agent or combination of toning agents.
• the processing web is maintained in intimate contact with the outermost hydrophilic colloid layer of the photographic element until development of developable silver halide is substantially complete, a dye image is formed in each of the exposed layers of the color photographic element, and at least a portion of the undeveloped silver halide has been dissolved from the emulsion layers and deposited in the processing web to form a black-and-white image.
• Precipitating agents for the purpose of this invention are either nuclei or development centers on which silver from a suitable silver halide complex is precipitated as metallic silver by physical development, or compounds which react with silver of the soluble silver halide complex to form an insoluble silver compound.
• the processing element is then separated from the substantially completely developed emulsion, which requires only a bleaching and fixing operation, or combined bleaching and fixing, followed by water washing, to render the color dye image permanent.
• the color photographic element comprises a support having at least one hydrophilic colloid silver halide emulsion layer containing a nondiffusible dye-forming coupler that reacts with oxidized aromatic primary amine color developing agent to form a nondifiusible dye image.
• the elements are multilayer, multicolor and contain a first hydrophilic colloid silver halide emulsion layer sensitive to light from a first region of the visible spectrum and a coupler that reacts with oxidized aromatic primary amine color developing agent to form a nondiffusible dye image of a first color, a second hydrophilic colloid silver halide emulsion layer sensitive to a second region of the visible spectrum that is different from the first region and a second coupler that reacts with oxidized aromatic primary amine color developing agent to form a nondiffusible dye image of a second color that is different from the first color dye, and'a third hydrophilic colloid silver halide emulsion layer sensitive to a third region of the visible spectrum that is different from the first and second regions and a third coupler that reacts with oxidized aromatic primary amine color developing agent to form a nondifi'usible dye image of a third color that is different from the first color and the second color.
• the hydrophilic colloid layers are hardened during manufacture.
• the dye-forming coupler is selected for a given silver halide emulsion so that it forms, upon reaction with oxidized color developing agent, a dye having a color that is complementary to the color of the light to which the silver halide emulsion is sensitive.
• a phenol or a naphthol cyan-dye-forming coupler is usually incorporated in a red-sensitive silver halide emulsion layer; a 5-pyrazolone or a ll-I-pyrazolo- [3,2-c]-s-triazole magenta-dye-forming coupler is usually incorporated in a green-sensitive silver halide emulsion layer; and an open-chain yellow-dye-forming coupler is incorporated in a blue-sensitive silver halide emulsion layer.
• These difierently sensitive silver halide emulsion layers are advantageously arranged on one side of a support in any order desired.
• Particularly advantageously orders are with the support coated in succession with a red-sensitive layer, a green-sensitive layer and a bluesensitive layer, and with the support coated in succession with a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer.
• the photographic elements advantageously contain additional layers, for example, a second red-sensitive layer contiguous to the first red-sensitive layer, a second green-sensitive layer contiguous to the first green-sensitive layer, a second blue-sensitive layer contiguous to the first blue-sensitive layer, non-sensitive, hydrophilic colloid light-filtering interlayers, etc.
• Photographic elements used to advantage in our process include those described by F'roehlich et al., U.S. Pat. 2,376,679; Vittum et al., U.S. Pat. 2,322,027; Fierke et al., U.S. Pat. 2,801,171; Godowsky, U.S. Pat. 2,698,794; Barr et al., U.S. Pat. 3,227,554; Graham, U.S. Pat.
• our process is used to produce in a color negative element and a web, a color negative and a silver positive, respectively, and in another embodiment our process is used to produce in a direct color reversal element and a web, a color positive and a silver negative, respectively.
• any of the photographic silver halide emulsions e.g., silver bromide, silver bromoiodide, silver chloride, silver chlorobromide, silver bromochloroiodide, etc., used in photography are used to advantage in the color elements used in our process including negative and direct-positive emulsions.
• the direct-positive emulsions advantageously comprise reduction and gold-fogged, cubic-shaped, silver halide grains having a uniform diameter frequency distribution with an average grain size in the range of from about 0.01 to about 2 microns, comprising at least about 50 mole percent bromide and preferably silver bromoiodide emulsions containing less than 10 mole percent iodide, as described in columns 2 through 8 .in Illingsworth, U.S. Pat. 3,501,305, issued Mar. 17, 1970.
• the emulsions used in the photographic elements are advantageously 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. Pat. 1,574,944, issued Mar. 2, 1926; Sheppard et al., U.S. Pat, 1,623,499, issued Apr. 5, 1927; and Sheppard et al., U.S. Pat. 2,410,689, issued Nov. 5, 1946.
• the emulsions can also be treated with salts of the noble metals, such as ruthenium, rhodium, palladium, iridium and platinum, as described in Smith et al., U.S. Pat. 2,448,060, issued Aug. 31, 1948 and as described in Trivelli et al., U.S. Pats. 2,566,245 and 2,566,263, both issued Aug. 28, 1951.
• the noble metals such as ruthenium, rhodium, palladium, iridium and platinum
• the emulsions are advantageously spectrally sensitized with cyanine and merocyanine dyes, such as those described in Brooker, U.S. Pats. 1,846,301 and 1,846,302, both issued Feb. 23, 1932; and 1,942,854, issued Jan. 9, 1934; White, U.S. Pat. 1,990,507, issued Feb. 12, 1935; Brooker and White, U.S. Pats. 2,112,140, issued Mar. 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued Jan. 10, 1950; and 2,739,964, issued Mar. 27, 1956; Brooker et al., U.S. Pat. 2,493,748, issued Jan. 10, 1950; Sprague, U.S. Pats.
• the emulsions advantageously contain speed-increasing compounds of the quaternary ammonium type of Carroll, U.S. Pat. 2,271,623, issued Feb. 3, 1942; Carroll et al., U.S. Pat. 2,288,226, issued June 30, 1942; and Carroll et al., U.S. Pat. 2,334,864, issued Nov. 23, 1943; and the polyethylene glycol type of Carroll et al., U.S. Pat. 2,708,- 162, issued May 10, 1955.
• the emulsions are advantageously chemically sensitized with gold salts as described in Waller et al., U.S. Pat. 2,399,083, issued Apr. 23, 1946, or stabilized with gold salts as described in Damschroder, U.S. Pat. 2,597,856, issued May 27, 1952; and Yutzy et al., U.S. Pat. 2,597,915, issued May 27, 1942.
• Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aurosulfobenzothiazole methochloride.
• Hydrophilio colloids used to advantage include gelatin, colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound.
• Some colloids which are advantageously used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe, U.S. Pat. 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 19-26% as described in Lowe et al., U.S. Pat. 2,327,808, issued Aug. 24, 1943; a water-soluble ethanolamine cellulose acetate as described by Yutzy, U.S.
• cyano-acetyl groups such as the vinyl alcohol-vinyl cyano-acetate copolymer as described in Unruh et al., U.S. Pat. 2,808,331, issued Oct. 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 Illingsworth et al., U.S. Pat. 2,852,- 382, issued Sept. 16, 1958.
• hydrophilic colloids described above are used in various layers of the photographic elements.
• the hydrophilic colloid layers are hardened either during manufacture or during the web processing step sufficiently so that their reticulation temperature and melting points, as defined herein previously, are higher than 65 C. and higher than 85 C., respectively, with hardening agents, such as aziridine hardeners, oxazolium hardeners, vinyl sulfone hardeners, mucochloric acid, aldehyde hardeners, e.g., glutaraldehyde, glutaraldehyde bisulfite, succinaldehyde, formaldehyde, epoxy ether hardeners, e.g., bis (2,3- epoxypropoxyethyl)ether, etc.
• hardening agents such as aziridine hardeners, oxazolium hardeners, vinyl sulfone hardeners, mucochloric acid, aldehyde hardeners, e.g., glutaraldeh
• the aziridine hardeners used to advantage include 1,3-bis(l-aziridinylsulfonyl)- propane, 1 (1 aziridinyl carbonyl) 3 (1 aziridinylsultonyl)-benzene and others described in Burness, U.S. Pat. 2,964,404, issued Dec. 13, 1960; N,N-trimethylenebis l-aziridine-carboxamide), N,N'-octamethylene bis-( 1- aziridine-carboxamide), toluene- 2,4 -bis(1-aziridine-carboxamide), N,N-tetramethylene bis(l aziridine carboxamide) and others described in Allen and Webster,
• the vinylsulfones used to advantage as hardeners for hydrophilic colloids in our photographic elements include hardening compounds having two vinylsulfonylalkyl groups linked to a single linking heteroatom (e.g., nitrogen atom, or oxygen atom) or radical, including hardeners such as, his (4-vinylsulfonylbutyl)ether, bis- (2 vinylsulfonylethyl)ether, bis(vinylsulfonylmethyl) ether, N-N-bis(2 vinylsulfonylethyl) n propylamine, N,N-bis(2 vinylsulfonylethyl) N ethyl N propylammonium tetrafluoroborate, and bis( 1 vinylsulfonylethyl)ether, etc., and other compounds of the formula: IX 1?.
• m is an interger of from 1 to 4
• Z is a heteroatom (e.g., nitrogen or oxygen) and R is hydrogen, or lower alkyl groups (e.g., methyl, ethyl, isopropyl, etc., which can in turn be further substituted), and hardening compounds having two or more vinylsulfonylalkyl groups (i.e., lower alkyl from 1 to 4 carbon atoms) attached to a plurality of tertiary or quaternary atoms and/or a plurality of ether oxygen atoms including typical compounds, such as:
• the light-sensitive layers of the photographic elements are advantageously coated on a wide variety of photographic emulsion supports.
• Typical supports used to advantage include cellulose nitrate film, cellulose acetate film, polyacetal film, polystyrene film, poly(ethylene terephthalate) film, polyethylene film and related films of resinous materials as well as paper, glass and others.
• any of the non-ditfusible color-forming couplers used in photographic elements are used to advantage in the photographic elements for our process.
• the phenol and naphthol cyan-dye-forming couplers used to advantage are those described by the following US. patents: 2,423,730, 2,474,293, 2,521,908, 2,725,291, 2,801,171, 3,253,294, etc.
• the ketomethylene yellow-dye-forming couplers used to advantage are those described in U.S. Pats. 2,298,443, 2,778,658, 2,801,171, 2,875,057, 3,253,924, 3,277,155, etc.
• Included among the 5-pyrazolone magenta-dye-forming couplers used to advantage are those described in U.S. Pats. 2,600,788, 2,801,171, 3,252,924, etc.
• Dispersing agents for color-forming couplers and the dispersing techniques used to advantage include those set forth in Jelley et al., U.S. Pat. 2,322,027; Mannes et al., U.S. Pat. 2,304,940; Fierke et al., U.S. Pat. 2,801,171, etc.
• the processing elements or processing webs of the pres ent invention comprise a hydrophilic organic colloid layer containing dispersed silver precipitating agent.
• the hydrophilic layers are employed alone if they have sutficient strength to be self-supporting, or if desired, they are coated on suitable supports.
• the supports and any subbing layers are preferably inert to the chemicals in the processing solution, and it is desirable in some cases that such supports be hydrophobic in nature as Well.
• Suitable hydrophilic organic colloids include gelatin, cellophane, poly(vinyl alcohol), sulfonated poly vinyl alcohol) derivatives [e.g., copolymers prepared from poly(vinyl alcohol) and sodium 2-sulfobenzaldehyde, copolymers prepared from poly(vinyl alcohol) and sodium 2-sulfobenzaldehyde and cyanoacetamidoacetaldehyde diethyl acetal, copolymers prepared from poly(vinyl alcohol) and sodium 4-methoxy- 3-sulfobenzaldehyde, copolymers prepared from poly- (viny alcohol) and 2,4-disulfobenzaldehyde, etc.], hydrolyzed cellulose acetate, cellulose ether phthalate, carboxylated rubber and similar materials.
• copolymers prepared from poly(vinyl alcohol) and sodium 2-sulfobenzaldehyde copolymers prepared from poly(vinyl alcohol) and sodium 2-s
• hydrophilic materials are gelatin and a copolymer made up of 80 percent acrylic acid and 20 percent ethyl acrylate.
• the hydrophilic colloid layer of the processing web is hardened so that its reticulation temperature and its melting point are higher than 65 C. and higher than 85 C., respectively (when measured as described herein previously) with any of the hardening agents described herein previously for hardening the hydrophilic colloid layers of the photographic element.
• it is advantageous to select hydrophilic colloids for the processing Web that will adhere well to the hydrophilic colloid in the emulsion layers of the photographic element during the first step of our process, but which separate readily from the processed film in Step 2.
• the silver precipitating agents incorporated in the hydrophilic colloid layer of the processing webs are physical development nuclei or chemical precipitants including (a) heavy metals, especially in colloidal form, and the salts of these metals; (b) salts, the anions of which form a silver salt less soluble than the silver halide of the photographic emulsion to be processed; or (c) non-diffusing polymeric materials with functional groups capable of combining with and insolubilizing silver ion.
• Suitable silver precipitating agents for use in the invention are disclosed in Rott, U.S. Pat. 2,352,014, Yutzy and Yackel, U.S. Pat. 2,740,717 and in Yackel et al., U.S. Pat. 3,020,- 155.
• useful silver precipitating agents include sulfides, selenides, polysulfides, polyselenides, thiourea and its derivatives, mercaptans, stannous halides, silver, gold, platinum, palladium, and mercury, colloidal sulfur, aminoguanidine sulfate, aminoguanidine carbonate, arsenous oxide, sodium stannite substituted hydrazines, xanthates, and the like.
• Polyvinyl rnercaptoacetate is an example of a non-diffusing polymeric silver precipitant.
• Heavy metal sulfides such as lead, silver, zinc, nickel, antimony, cadmium and bismuth sulfides are useful, particularly the sulfides of lead and zinc alone or in admixture, or complex salts of these with thioacetamide, dithiooxamide, or dithio-biuret.
• the heavy metals and the noble metals particularly in colloidal form are especially effective.
• Other silver precipitating agents will occur to those skilled in the art.
• the average particle size of these silver precipitating agents is advantageously in the range of from 7 to 2500 angstrom units.
• the processing web advantageously has in the range of from about 3 mg./m. to about 1290 mg./m. of silver precipitating agent coated in it.
• the processing elements or webs of the invention take any suitable form or shape.
• they consist of pads, sheets, strips or webs of hydrophilic material either unsupported or coated on suitable supports such as glass, metal, paper, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, cellulose esters, or the like.
• suitable supports such as glass, metal, paper, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, cellulose esters, or the like.
• An especially useful web for producing reflection transfer images is that disclosed in U.S. Pat. 3,415,647.
• Preferred processing solution imbibants comprise one or more aromatic primary amine color developing agents, an amine sulfur dioxide addition product, and optionally, an additional silver halide solvent, water and, when necessary, a hardening agent.
• Aromatic primary amine color developing agents useful in the practice of our invention are p-phenylenediamine derivatives, such as, those given in Bent et al., J. Am. Chem. Soc., 73, 3100 (1951). Especially preferred agents are:
• An operable range of developing agent concentration is from about 2 g. to about 100 g./l. and a preferred range is from about 10 g. to about 50 g./l.
• R and R each represent a member independently selected, such as hydrogen, methyl, ethyl, aminoethyl, hydroxyethyl and together they represent the nonmetallic atoms required to complete a morpholino group or a piperidino group and R represents a member such as hydrogen, 2-hydroxyethyl, 1-methyl-2-hydroxyethyl, 1,1-dimethyl-2-hydroxyethyl and 5-hydroxypentyl such that no more than two of R, R and R represent hydrogen.
• Typical amines used in the addition products include Z-aminoethanol, 2-methylaminoethanol, 2-dimethylaminoethanol, 2-ethylaminoethanol, 2-diethylaminoethanol, 2,2',2"-nitrilotriethanol, 2-(2-aminoethylamino)ethanol, 2,2'-iminodiethanol, 5-diethylamino-2-pentanol, 2-amino-2-rnethyl-1- propanol, morpholine and piperidine, among others.
• a preferred amine-sulfur dioxide addition product is prepared in the following manner. Sulfur dioxide gas is slowly bubbled through one mole of the preferred amine, 2-methylaminoethanol, with adequate stirring until it absorbs the equivalent of 0.5 mole of sulfur dioxide. The resulting 2-methylamino-ethanol-sulfur dioxide addition product contains the equivalent of 30 percent sulfur dioxide, by weight, or 33 mole percent. It will be understood that the ratio of S0 to amine can be increased or decreased from that just given as required to bring the pH of the processing solution to the desired level.
• An operable amineSO concentration range is from about 5 ml. to about 300 ml./l. with from about 2.5% to 35% by weight SO; and a preferred range is from about 10 ml. to about 200 ml./l. with from about 5% to about 33% by Weight S0
• These compounds usually supply the alkali needed as well as supply at least a part of the silver halide solvent.
• the processing solution preferably has a relatively low salt content so that it is readily absorbed by the hydrophilic colloid layers for processing.
• the developing capability of the processing solution is preferably relatively high in capacity and rate so development is essentially completed before any appreciable transfer of complexed silver to the processing web occurs.
• a silver halide solvent such as, up to about 50 g./l. of an alkali metal thiosulfate (e.g., sodium thiosulfate, potassium thiosulfate, etc.), an alkali metal thiocyanate (e.g., sodium thiocyanate, potassium thiocyanate, etc.), an alkali metal selenocyanate, thioglycerol, aminoethanethiols, p,p'-dithiasuberic acid, etc.
• an alkali metal thiosulfate e.g., sodium thiosulfate, potassium thiosulfate, etc.
• an alkali metal thiocyanate e.g., sodium thiocyanate, potassium thiocyanate, etc.
• an alkali metal selenocyanate e.g., sodium thiocyanate, potassium thiocyanate, etc.
• the pH of the developer solution is advantageously in the range of from about 8.5 to about 11.5 and preferably in the range of from about 9 to 11.
• Toning agents suitable for incorporation in the processing solution to increase the neutrality of image tone of the image transferred to the processing web include those described in US. Pats. 3,017,270 and 3,314,789.
• toning agents When toning agents are desired it is advantageous to use them in the concentration range of from about .002 to about 1.0 g./l. and preferably in the range of from about .01 to .25 g./l.
• onium compounds are desired, they are used in the concentration range of from about .05 to about 2.0 g./l. and preferably in the range of from about .1 to about 1.0 g./l.
• the processing solution containing the aromatic primary amine color developing agent, the alkali, and silver halide solvent is imbibed into the hydrophilic colloid layer containing the silver precipitating nuclei prior to contacting the web and the light-exposed color negative element. It is advantageous to imbibe in the range of from about 48 g. to about 215 g. of the processing solution per m? of the processing web, and preferably in the range of from about 65 g. to about 100 g. of solution per m? of the web. Imbibition usually takes in the range of from 1 minute to 30 minutes in the range of temperature from about 20 C. to about 50 C. A minimum amount of water or moisture is utilized in the imbibed processing solution to facilitate the physical handling of the web, but suflicient in amount to effect the photographic processing reactions.
• An operable web processing time is in the range of from about 3 to 60 minutes with a preferred range of from about 5 to about 20 minutes.
• the process is carried out at temperatures in the range of from about 20 C. up to about 38 C., the temperature not being particularly critical. It is found, however, that even at ambient temperature (20 C.), conventional color films exhibit physical damage under the processing conditions involved in web processing and cannot be used unless a sufficient amount of a hardening agent is imbibed in the processing web to harden the hydrophilic colloid layers of element and web while they are laminated so that their reticulation temperature is greater than 65 C. and their melting point is greater than 85 C. by the time the element and web are to be separated from each other.
• the preferred color elements used for our process have hydrophilic colloid layers hardened sufficiently during manufacture to have reticulation temperatures above 65 C. and melting points above 85 C. (when measured in distilled Water as defined herein previously), and do not exhibit any physical damage from our web process.
• EXAMPLE 1 A multilayer color negative film hardened with bis[2- (2-vinylsulfonylethoxy)ethyl]sulfone is prepared as follows: On a cellulose acetate photographic film support, the following layers are coated, beginning at the support:
• a gray-colored gelatin antihalation layer containing bleachble dye (1) A gray-colored gelatin antihalation layer containing bleachble dye.
• gelatin layers are hardened so that the reticulation temperature and the melting point measured as defined herein previously are 83 C. and greater than two minutes at 100 C., respectively.
• the film just described is exposed to an original light image and developed in contact with a web of the following composition: A polyethylene terephthalate support is coated with gelatin at 20.4 g./m. containing as silver precipitating nuclei 9.7 mg./m. of nickel sulfide and 9.7 mg./m. of silver iodide prepared as described in Example 1 of British Pat. 1,080,781.
• a spreading agent and hardener bis[2-(2-vinylsulfonylethoxy)ethyl]sulfone are included in the coating so that it has a reticulation temperature and a melting point measured as described previously of greater than 65 C. and greater than 85 C., respectively.
• the web is soaked in the following imbibant solution for ten minutes at 38 C. to imbibe about 86 g. of the solution per m 2-methylaminoethanol-SO addition product ml 4 amino-3-methyl-N-ethyl-N-,B-hydroxyethylaniline sulfate g Sodium thiosulfate g Water to make 1 liter.
• the processed negative color film is printed onto a reflection color print material using conventional techniques to produce upon conventional color processing a print of excellent color fidelity and definition.
• EXAMPLE 2 An imagewise exposed sample of the color negative film described in Example 1 is developed in contact with a web of the same composition as described in Example 1 which is soaked in the followed imbibant solution for one minute at 38 C.:
• the web is found to contain about 80 g. of the imbibant per m3 following the l-minute soak.
• the films are separated as in Example 1 to give in the web a good positive black-and-white image reproduction and in the photographic element an excellent color negative and silver negative image reproduction.
• the photographic element is water washed, then bleached and fixed as described in Example 1 to remove the silver image and residual silver halide and leave a permanent three-color negative image reproduction of the original. This color negative is then printed onto a reflection print element as described in Example 1 to give upon conventional color processing an excellent color print reproduction of the original light image.
• EXAMPLE 4 Examples 1, 2 and 3 are repeated, but using a processweb as described in Example 1 of US. Pat. 3,415,647 is used in place of the film support used in immediate Examples 1, 2 and 3. Good reflection positive black-andwhite reproductions are obtained in the processing web and excellent color negatives in the processed photo graphic element that are used to produce high quality color prints.
• Example 1 is repetated, but imbibing in the processing web a processing solution from which the sodium thiosulfate is omitted. An excellent black-and-white positive is obtained in the processing web and an excellent color negative is obtained in the color negative element. Excellent color prints are made from the color negative.
• Example 1 is repeated, but adding to the processing solution imbibant of Example 1 of 0.2 g./l. of 2-hydroxy- 4-thiatetradecyl-trimethylammonium p-toluene sulfonate and 0.05 g./l. of 3-mercapto-1,2,4-triazole. Excellent black-and-white positive, color negative and color print are obtained.
• Example 1 is repeated, but substituting 150 m./l. of 2,2'-iminodiethanol-SO addition product (13% S0 by weight) for the 2-methylaminoethanol-SO addition product in the Web imbibant solution of Example 1. With this substitution, the pH of the imbibant solution is about 9.0. The quantity of solution imbibed under the conditions used in Example 1 is reduced from about 86 g./m. to about 64 g./rn. A useful image is produced in the web and a color negative, similar to that of Example 1, is produced.
• Example 3 is repeated, but substituting for the color developing agent used in Example 3, an equimolar amount of 4-arnino-3-methyl-N-ethyl-N-fl-sulfoethylaniline.
• Example 3 is again repeated, but substituting for the developing agent an equimolar amount of 4-amino-N-ethyl-N-,8;ydihydroxypropylaniline.
• Example 3 is again repeated, but substituting for the developing agent used in Example 3 an equimolar amount of 4-amino-N-ethyl-N-(Z-methoxyethyl)-m-toluidine-dihydrochloride.
• black-and-White positive image, color negatives and color prints are obtained of quality comparable to the quality obtained in Example 3.
• Example 1 is repeated, but using a conventional color negative film in which the emulsion layers are found to have a reticulation temperature of about 23 C. and a melting point of about 48 C. when measured as described herein previously.
• the hydrophilic colloid layers of the color negative are found to be physically damaged by the web process and of no value.
• This example is outside our invention, since the hydrophilic colloid emulsion layers of the color negative material do not have reticulation temperatures above C. and melting points above C.
• Example 1 is repeated, but (1) using a conventional color negative film in which the emulsion layers are found to have a reticulation temperature of about 23 C. and a melting point of about 48 C. when measured as described herein previously before processing and (2) adding 2 g./1. of glutaraldehyde bisulfite addition complex to the imbibant solution used in Example 1.
• the gelatin layers in the color negative element and in the processing web are hardened during the fifteen-minute processing step in which the negative element and web are contacted so that when separated, the gelatin layers are found to have reticulation temperatures greater than 65 C. and melting points greater than 85 C. and there is no physical damage caused in the negative or web when they are separated.
• a good color negative is produced in the element which is used after the bleaching and fixing steps, to make a good color print as described in Example 1.
• appropriate amounts of other hardening agents described herein previously are advantageously used in place of glutaraldehyde bisulfite in Example 10 to give good color negatives and silver positives.
• Example 1 is repeated, but using the direct-positive photographic silver halide emulsions with nondifiusible couplers described in Coatings 3, 2 and 1 in Example III in Illingsworth, US. Pat. 3,501,305, issued Mar. 17, 1970, in place of the red-sensitive layer, the green-sensitive layer and blue-sensitive layers, respectively, used in the element of immediate Example 1.
• the gelatin in the web and the gelatin in the layers of the direct-positive photographic element are hardened during manufacture so that they have reticulation temperatures greater than 65 C. and melting points greater than 85 C.
• the direct-positive photographic element is exposed and processed as described in Example 1 to produce a silver negative image reproduction in the processing web and a silver positive and a dye positive image in the direct-positive photographic element. Removal of the silver and residual silver halide from the web-processed direct-positive color element leaves a good, stable color positive image.
• Example 11 is repeated, but (1) using direct-positive silver halide emulsion layers that have a reticulation temperature of about 23 C. and a melting point of about 48 C. when measured as described herein previously before processing and (2) adding 2 g./1. of glutaraldehyde bisulfite addition complex to the imbibant solution used in Example 1.
• the gelatin layers in the direct-positive eemperent and in the processing web are hardened during the fifteen-minute processing step in which the direct-positive element and web are contacted so that when separated, the gelatin layers are found to have reticulation temperatures greater than 65 C. and melting points greater than 85 C. and there is no physical damage caused in the directpositive or web when they are separated.
• a good color positive is produced in the element that is stabilized by removal of silver and residual silver halide as described in Example 1.
• EXAMPLE 13 G Ammonium ethylenedinitrilotetra-acetato ferrate (III) 145 Ammonium thiosulfate 148 Ammonium sulfite 12 Water to 1 liter.
• An alternative procedure for producing a black andwhite image in a web material and a dye image in a radiation-sensitive color material is as follows: The diffusion transfer process that has been described is used, but a developing agent or combination of developing agents that produce only silver images, rather than silver and dye images, in the color material are incorporated in the imbibant solution. The p-phenylenediamine type developing agent is omitted. Following the diffusion transfer step, the color material bearing a silver image is fixed to remove silver halide, and then treated with a rehalogenizing bleach to convert the silver image to silver halide. The silver halide image is given an overall white light exposure sufficient to completely fog the silver halide, and is then processed in a conventional color process, such as that described in Example 1 of US. Pat. 2,956,879 to produce dye images in the color material.
• a color process for an imagewise-exposed photographic element for producing during a single processing step a. silver and a dye image in said element and producing a transfer silver image in a hydrophilic colloid processing web coated on a separate support, said photographic element comprising a support coated on one side with at least one hydrophilic colloid layer containing dispersed silver halide grains and a non-diffusible dye-forming coupler that reacts with an oxidized aromatic primary amine color developing agent to produce a nonditfusible dye, said hydrophilic colloid in said processing web and in said element being hardened either during manufacture or during process step (1) below to have a reticulation temperature greater than 65 C. and a melting point greater than C., said process comprising the steps:
• a color process for an imagewise-exposed photographic element for producing during a single development step a silver and a dye image in said element and producing a transfer silver image in a hardened hydrophilic colloid processing web having a reticulation temperature greater than 65 C. and a melting point greater than 85 C. coated on a separate support, said photographic element comprising a support coated on one side with at least one hardened hydrophilic colloid layer having a reticulation temperature greater than 65 C. and a melting point greater than 85 C. containing dispersed silver halide grains and a nondiffusible dye-forming coupler that reacts with an oxidized aromatic primary amine color developing agent to produce a nonditfusible dye, said process comprising the steps:
• said hydrophilic colloid processing web which contains silver precipitating agent, an alkali, an aromatic primary amine color developing agent and a silver halide solvent until substantially all developable silver halide grains in said photographic element are developed to a silver image and a nondifiusible dye image, and at least a part of the undeveloped silver halide grains in areas not color developed in said photographic element are dissolved by said silver halide solvent and transferred imagewise to said hydrophilic colloid processing web where a silver image is formed on said silver precipitating agent, and
• a color process for an imagewise-exposed photographic element for producing during a single processing step a silver and a dye image in said element and producing a transfer silver image in a hydrophilic colloid processing web coated on a separate support, said photographic element comprising a support coated on one side with at least one hydrophilic colloid layer containing dispersed silver halide grains and a nondifiusible dye-forming coupler that reacts with an oxidized aromatic primary amine color developing agent to produce a nondifiusible dye, said process comprising the steps:
• a color process for an imagewise-exposed photographic element for producing a dye image in said element and producing a transfer silver image in a hardened hydrophilic colloid processing web having a reticulation temperature greater than 65 C. and a melting point greater than 85 C.
• said photographic element comprising a support coated on one side with at least one hardened hydrophilic colloid layer having a reticulation temperature greater than 65 C. and a melting point greater than 85 C. containing dispersed silver halide grains and a nonditfusible dye-forming coupler that reacts with .an oxidized aromatic primary amine color developing agent to prodtuce a nondifiusible dye, said process comprising the s eps:
• step (3) contacting the silver image and any residual silver halide in said photographic element from step (2) with a silver bleach bath comprising a photographic silver oxidizing agent until the silver is converted to a silver salt; and
• a color process for an imagewise-exposed photographic element for producing a dye image in said element and producing a transfer silver image in a hardened hydrophilic colloid processing web said photographic element comprising a support coated on one side with at least one hardened hydrophilic colloid layer having a reticulation temperature greater than 65 C. and a melting point greater than 85 C. containing dispersed silver halide grains and a nonditfusible dye-forming coupler that reacts with an oxidized aromatic primary amine color developing agent to produce a nondiffusible dye, said process comprising the steps:
• said hydrophilic colloid processing web which contains silver precipitating agent, an alkali, an aromatic primary amine color developing agent and a silver halide solvent until substantially all developable silver halide grains in said photographic element are developed to a silver image and a nondiflfusible dye image, and at least a part of the undeveloped silver halide grains in areas not color developed in said photographic element are dissolved by said silver halide solvent and transferred imagewise to said hydrophilic colloid processing web where a silver image is formed on said silver precipitating agent;
• step (3) contacting said silver image and any residual silver halide in said photographic element from step (2) with a combined bleach-and-fix solution comprising a silver oxidizing agent and a silver salt solvent until said silver and said silver salt are dissolved and diffused from said photographic element so said dye image is unobstructed and made permanent.
• a combined bleach-and-fix solution comprising a silver oxidizing agent and a silver salt solvent until said silver and said silver salt are dissolved and diffused from said photographic element so said dye image is unobstructed and made permanent.
• a color process for an imagewise-exposed photographic element for producing during a single processing step a silver negative and a color negative image in said element and producing a transfer silver positive image in a hydrophilic colloid processing web coated on a separate support, said photographic element comprising a support coated on one side with at least one hydrophilic colloid layer containing dispersed silver halide grains and a nondiffusible dye-forming coupler that reacts with an oxidized aromatic primary amine color developing agent to produce a non-ditfusible dye, said hydrophilic colloid in said processing Web and in said element being hardened either during manufacture or during process step (1) below to have a reticulation temperature greater than 65 C. and a melting point greater than 85 C., said process comprising the steps:
• said hydrophilic colloid processing web which contains silver precipitating agent, an alkali, an aromatic primary amine color developing agent and a silver halide solvent until substantially all developable silver halide grains in said photographic element are developed to a silver negative image and a nondiffusible dye negative image, and at least a part of the undeveloped silver halide grains in areas not color developed in said photographic element are dissolved by said silver halide solvent and transferred imagewise to said hydrophilic colloid processing web where a silver positive image is formed on said silver precipitating agent, said processing web containing a hardening agent when said hydrophilic colloid in said photographic element and said Web are not hardened during manufacture; and
• a color process for an imagewise-exposed multilayer, multicolor photographic element for producing during a single processing step a silver negative and a color negative image in said element and producing a transfer silver positive image in a hardened hydrophilic colloid processing Web having a reticulation temperature greater than 65 C. and a melting point greater than 85 C.
• said photographic element comprising a support coated on one side with a first hardened hydrophilic colloid silver halide emulsion layer sensitive to light from a first region of the visible spectrum and a coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondifiusible dye image of a first color, a second hardened hydrophilic colloid silver halide emulsion layer sensitive to a second region of the visible spectrum that is different from said first region and a second coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondiffusible dye image of a second color that is different from said first color dye, and a third hardened hydrophilic colloid silver halide emulsion layer sensitive to a third region of the visible spectrum that is different from said first region and said second region and a third coupler that reacts with oxidized aromatic primary amine color developing agent to form a nondiffusible dye image of a third color that is different from said first color
• a color process for an imagewise-exposed multilayer, multicolor photographic element for producing during a single processing step a silver negative and a dye negative image in said element and producing a corre sponding transfer silver positive image in a hardened hydrophilic colloid processing web having a reticulation temperature greater than 65 C. and a melting point greater than 85 C.
• said photographic element comprising a support coated on one side with a hardened hydrophilic colloid layer containing red-sensitive silver halide grains and a nondiflfusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondiifusible cyan dye image, a hardened hydrophilic colloid layer containing green-sensitive silver halide grains and a nondiffusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondiffusible magenta dye, a hardened hydrophilic colloid layer containing blue-sensitive silver halide grains and a nondiffusible coupler that reacts with an ozxidized aromatic primary amine color developing agent to form a nondifiusible yellow dye, said hardened hydrophilic colloid layers in said photographic element each having a reticulation temperature greater than 65 C. and a melting point greater than 85 C., said process comprising the steps:
• a color process for an imagewise-exposed multilayer, multicolor direct-positive photographic element for producing during a single processing step a silver positive and a color positive image in said element and producing a corresponding transfer silver negative image in a hardened hydrophilic colloid processing web having a reticulation temperature greater than 65 C. and a melting point greater than C.
• said photographic element comprising a support coated on one side with a first hardened hydrophilic colloid directpositive silver halide emulsion layer sensitive to light from a first region of the visible spectrum and a coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondifiusible dye image of a first color, a second hardened hydrophilic colloid directpositive silver halide emulsion layer sensitive to a second region of the visible spectrum that is different from said first region and a second coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondifiusible dye image of a second color that is different from said first color dye, and a third hardened hydrophilic colloid direct-positive silver halide emulsion layer sensitive to a third region of the visible spectrum that is different from said first region and said second region and a third coupler that reacts with oxidized aromatic primary amine color developing agent to form a nondifiusible dye image of a
• a color process for an imagewise-exposed multilayer, multicolor direct-positive photographic element for producing during a single processing step a silver positive and a dye positive image in said element and producing a corresponding transfer silver negative image in a hardened hydrophilic colloid processing web having a reticulation temperature greater than 65 C. and a melting point greater than 85 C.
• said photographic element comprising a support coated on one side with a hardened hydrophilic colloid layer containing red-sensitive direct-positive silver halide grains and a nondiffusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondiffusible cyan dye image, a hardened hydrophilic colloid layer containing green-sensitive directpositive silver halide grains and a nonditIusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondifiusible magenta dye, a hardened hydrophilic colloid layer containing bluesensitive direct-positive silver halide grains and a nondiffusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondiffusible yellow dye, said hardened hydrophilic colloid layers in said photographic element each having a reticulation temperature greater than 65 C. and a melting point greater than 85 C., said process comprising the steps:
• hydrophilic colloid processing web contains a p-phenylenediamine color developing agent and an amine-sulfur dioxide addition product as the alkali and silver halide solvent.
• hydrophilic colloid processing web contains a solution containing in the range of from about 2 g./l. to about 100 g./l. of a color developing agent selected from the class consisting of 4-amino-3-methyl-N-ethyl-N-fi-hydroxyethylaniline sulfate,
• 4-amino-N-ethyl-N-[3-y-dihydroxypropylaniline and 4-amino-N-ethyl-N- (Z-methoxyethyl) -m-toluidine dihydrochloride contains in the range of from about 5 g./l. to about 300 g./l. of Z-methylaminoethanol-sulfur dioxide addition product and said solution has a pH in the range of from about 8.5 to about 11.5.
• a color process for an imagewise-exposed multilayer, multicolor photographic element for producing during a single processing step a silver and a dye image in said element and producing a transfer silver image in a hardened gelatin processing web coated on a separate support, said photographic element comprising a support coated on one side with a hardened gelatin layer containing red-sensitive silver bromoiodide grains and a nondiifusible coupler that reacts with an oxidized aromatic primary amine color developng agent to form a nondiffusible cyan dye image, a hardened gelatin layer containing green-sensitive silver bromoiodide grains and a nondiifusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondifiusible magenta dye, a hardened gelatin layer containing blue-sensitive silver bromoiodide grains and a nondifiusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondiffusible yellow dye, each of said hardened
• a color process for an imagewise-exposed multilayer, multicolor photographic element for producing during a single processing step a silver and a dye image in said element and producing a transfer silver image in a hardened gelatin processing web having a reticulation temperature greater than 65 C.
• said photographic element comprising a support coated on one side with a hardened gelatin layer containing red-sensitive silver bromoiodide grains and a non-diifusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondiffusible cyan dye image, a hardened gelatin layer containing green-sensitive silver bromoiodide grains and a nondiffusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondiffusible magenta dye, a hardened gelatin layer containing blue-sensitive silver bromoiodide grains and a nondiifusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondiffusible yellow dye, each of said hardened gelatin layers in said photographic element having a reticulation temperature of 83 C. and a melting point of greater than C., said process comprising the steps:
• a color process for an imagewise-exposed multilayer, multicolor photographic element for producing during a single processing step a silver negative and a dye negative image in said element and producing a transfer silver positive image in a hardened gelatin processing web coated on a separate support, said photographic element comprising a support coated on one side with a hardened gelatin layer containing red-sensitive silver bromoiodide grains and a nondiffusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondilfusible cyan dye image, a hardened gelatin layer containing green-sensitive silver bromoiodide grains and a nondiflusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondifiusible magenta dye, a hardened gelatin layer containing blue-sensitive silver bromoiodide grains and a nondiffusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondiffusible yellow dye, each of said hardened
• gelatin layer of said photographic element for fifteen minutes at 20 C. with said gelatin layer of said processing web which contains 20.4 g./m. of nickel sulfide-silver iodide silver precipitating nuclei; an aqueous solution of pH 10.0 containing 100 ml./l. of 2 methylaminoethanol --SO addition product with 30% S 40 g./l. of 4-amino-3- methyl-N-ethyl-N-p hydroxyethylaniline sulfate and g./l.
• a color process for an imagewise-exposed multilayer, multicolor photographic element for producing during a single processing step a silver negative and a dye negative image in said element and producing a transfer silver positive image in a hardened gelatin processing Web having a reticulation temperature greater than 65 C.
• said photographic element comprising a support coated on one side with a hardened gelatin layer containing red-sensitive silver bromoiodide grains and a nondifiusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nonditfusible cyan dye image, a hardened gelatin layer containing green-sensitive silver bromoiodide grains and a nondiffusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nonditfusible magenta dye, a hardened gelatin layer containing blue-sensitive silver bromoiodide grains and a nonditfusible coupler that reacts with an oxidized aromatic primary amine color developing agent to form a nondiffusible yellow dye, each of said hardened gelatin layers in said photographic element having a reticulation temperature of 83 C. and a melting point of greater than 100 C., said process comprising the steps:

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• 1971
  • 1971-01-25 US US109719A patent/US3689272A/en not_active Expired - Lifetime
  • 1971-12-07 CA CA129,522A patent/CA959696A/en not_active Expired
• 1972
  • 1972-01-25 GB GB347872A patent/GB1381054A/en not_active Expired
  • 1972-01-25 FR FR7202307A patent/FR2123376B1/fr not_active Expired

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