US3671244A - Process for forming dye images - Google Patents

Process for forming dye images Download PDF

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Publication number
US3671244A
US3671244A US31352A US3671244DA US3671244A US 3671244 A US3671244 A US 3671244A US 31352 A US31352 A US 31352A US 3671244D A US3671244D A US 3671244DA US 3671244 A US3671244 A US 3671244A
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Prior art keywords
metal
image
salt
acrylate
weight
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Expired - Lifetime
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US31352A
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English (en)
Inventor
Vernon L Bissonette
Jerry B Miller
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/56—Processes using photosensitive compositions covered by the groups G03C1/64 - G03C1/72 or agents therefor
    • 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
    • G03C5/40—Chemically transforming developed images
    • G03C5/46—Toning

Definitions

  • This invention is related to photography, photographic elements, compositions for use in photographic processing and photographic processes for forming high density dye images from photographic metal images.
  • a photographic element containing at least one terpolymer and a metal image with a standard oxidation potential more positive than --0.98 volt is brought into contact with an aqueous solution of a tetrazolium salt (T-salt) until the T-salt oxidizes the metal image to a metal ion and the T-salt is reduced to the corresponding formazan dye in situ.
  • T-salt is used in the presence of a metal complexing ligand that forms a metal complex.
  • This metal complexing ligand is either 1) a separate compound in the T-salt solution or (2) a moiety of the T-salt molecule, or the complexing function is filled by a combination of 1) and (2).
  • the formazan dye which is produced from the T-salt is nondiffusible and replaces at least a portion of the metal image.
  • Particularly useful terpolymers are prepared by terpolymerizing at least one unsaturated polymerizable compound containing one or more groups with a different monomer having the formula:
  • Useful terpolymers comprise at least one unit of a monomer having the above formula with at least one other ethylenically unsaturated polymerizable monomer which forms addition polymers, such as vinyl esters, amides, nitriles, ketones, halides, ethers, alpha-beta-unsaturated acids or esters thereof, olefins, diolefins and the like, as exemplified by acrylonitrile, methacrylonitrile, styrene, alphamethylstyrene, acrylamide, vinyl chloride, methyl vinyl ketone, fumaric, maleic and itaconic esters, Z-chloroethyl vinyl ether, acrylic acid, sodium methacryloyloxyethyl sulfate, methacrylic acid, difnethylaminoethyl methacrylate, 4,4,9-trimethyl-8-oxo-7
  • R is hydrogen or alkyl as defined previously and M is a cation as described previously.
  • the preferred latex terpolymers Containing sulfoester units contain in polymerized form at least about 65% by weight of monomer (1), at least about 3% by weight of sulfoester monomer (2) and at least 2% by weight of monomer (3).
  • the preferred solution terpolymers containing acrylic acid units contain in polymerized form, at least 65% by weight of monomer (l), at least about 10% by weight of acrylic acid and at least about 2% by weight of monomer (3).
  • the ethylenically unsaturated polymerizable monomers having Formula I are prepared using any procedure suitable for this purpose.
  • the reaction of acid chlorides, acid anhydrides or mixed anhydrides containing active methylene groups with acrylic esters containing hydroxyalkyl substituents are employed.
  • a preferred synthesis for preparing the esters having an active methylene group in the ester moiety involves the reaction of a hydroxyalkyl ester of acrylic or an alpha-alkyl acrylic acid with diketene or cyanoacetyl chloride.
  • esters having active methylene groups in the alpha-substituent in the above formula can be obtained by reacting the alphahydroxyalkyl substituted acrylic esters with diketene or cyanoacetyl chloride. Such reactions are not particularly pressure sensitive and, therefore, can be carried out at atmospheric, superatmospheric or subatmospheric pressure.
  • the temperature range is subject to wide variation depending, for example, upon the particular reactants employed, solvents and like considerations, but generally temperatures up to about 100 C. and often temperatures in the range of about 35 to about 100 C. are suitable.
  • emulsions are advantageously coated on any of the usual supports, including paper, glass, polymeric films, e.g., cellulose acetate film, polyvinyl acetal film, polystyrene film, polypropylene film and other polyolefin films, polycarbonate film, polyethylene terephthalate film and other polyester films.
  • polymeric films e.g., cellulose acetate film, polyvinyl acetal film, polystyrene film, polypropylene film and other polyolefin films, polycarbonate film, polyethylene terephthalate film and other polyester films.
  • X represents an anion (e.g., chloride, iodide, bromide, thiocyanate, thiosulfate, sulfate, paratoluenesulfonate, me'thylsulfate, ethylsulfate, nitrate, acetate, perchlorate, perborate, sulfite, hydroxide, carbonate, etc.),
  • D represents a divalent aromatic group (e.g., a phenylene, diphenylene, naphthalene, phenylmethylphenyl, etc.); and E represents a divalent group such as an alkylene group (e.g., methylene, ethylene, propylene, butylene, etc.), an arylene group (e.g., phenylene naphthalene, diphenylene, etc.), an arylene alkylene group, for example, a pheny
  • Tetrazolium salts used to advantage according to our invention include the following representative compounds: T-salt No.: T-Salt name 1 2- (benzolthiazol-Z-yl -3-phenyl-5- (o-chlorophenyl)-2H-tetrazoliurn chloride 2 2-(4,5-dimethylthiazol-2-yl)-3,5-dipheny1-2H- tetrazolium bromide 3 3,5-diphenyl-2-(4-phenylthiaZol-2-yl)-2H- tetazolium iodide 5-(4,5-dimethylthiazol-2-yl)-2,3-diphenyl-2I-I- tetrazolium chloride 2- (benzothiazol-Z-yl) -3-phenyl-5-(thien-2-y1) -2H- tetrazolium chloride 2,3-diphenyl-5- (pyrid-Z-yl)-2H-tetrazolium bro
  • T-salt Formazan Dye Any liquid that is a silver complexing agent is advantageously used that produces a silver ion complex.
  • ligands used to advantage are the following typical examples: water-soluble thiosulfates (e.g., sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, etc.), thiourea, ethylenethiourea, a water-soluble thiocyanate (e.g., sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate), a water-soluble sulfur containing dibasic acid.
  • water-soluble diols used to advantage include those having the formula:
  • X and X represent oxygen or sulfur, such that when X represents oxygen, X represents sulfur and when X represents sulfur, X represents oxygen;
  • 0, d, e, f and g each represent an integer of from 1 to 15, such that the sum of c+d+e+f+g represents an integer of from 6 to to 19, and such that at least one third of the total of all the Xs plus all the X s represent sulfur atoms and at least two consecutive Xs and/or X s in the structure of the compound are sulfur atoms.
  • Typical diols include the following: 1) 3,6-dithia-1,8-octanediol HOCH CH SCH CH SCH CH OH (2) 3,6,9-trithia-l,ll-undecanediol H0CH CH SCH CH SCH CH SCH CH OH (3) 3,6,9,12-tetrathia-1,l4-tetradecanediol HO(CH CH S) CH CH OH 12 (4) 9-oxa-3,6,9,12,IS-tetrathia-1,17-heptadecanediol HO (CH CH S) CH CH O (CH CH S CH CH OH 5) 9,12-dioxa-3,6,15,18-tetrathia-1,20-eicosanediol HO (CH CI-I S) CH CH O) 2 (CH CH S CH CH 0H (6) 3,6-dioxa-9,l2-dithia-l,14-te
  • HOOCCH (SCH CH SCH COOH in which q represents an integer of from 1 to, and including, 3 and the alkali metal and ammonium salts of said acids.
  • Typical illustrative examples include:
  • concentration of the T-salt and the ligand in our compositions can be varied considerably, with an operable range of concentrations extending from the solubility limit of the T-salt and the solubility limit of the ligand down to a minimum concentration where the overall reaction potential for the specific
  • T- salt Solution 1 having the composition:
  • T-SALT SOLUTION 1 Water ml 600 NEI2HPO4 -g- 4J2 2 g 200 Thiourea g 10 2,3,5-triphenyl-ZH-tetrazolium chloride g- 10 H2O to 1 1.
  • the D of the formazan dye image replacing the silver image is measured for each of the treated elements.
  • Table 1 shows the binder used, the formazan dye Dmax, and the image D amplification (i.e., Dye D jsilver D for each element.
  • EXAMPLE 3 Five photographic X-ray elements, Y and Z (both outside our invention), E, F and G (of our invention) are prepared. The transparent support of each element is coated on both sides with its own emulsion. Each of the emulsion layers have the same silver bromoiodide coated at 175 mg./ft. of silver and the binder indicated in Table 3. The elements are exposed and black-and-white processed as described in Example 1. After measuring the silver D fs, the elements are treated for 15 seconds at 100 F. in the T-salt Solution 2 having the composition:
  • Example 1 is repeated but with the T-salt solution at 75 F., instead of F. The results are substantially the same as obtained in Example 1. This demonstrates that our invention operates over a wide range of T-salt solution temperatures.
  • Example 1 is repeated, using a modified T-salt Solution 1 in which the thiourea is replaced by an equimolar amount of ammonium thiocyanate.
  • Elements A and B of our invention produce formazan dye images that are superior to the formazan dye images produced in element W outside our invention.
  • Example 1 is repeated, using a modified T-salt Solution 1 in which the thiourea is replaced by an equimolar amount of 3,6-dithia-l,8-octanediol.
  • Our elements A and B produce formazan dye images that have D amplifications that are substantially higher than obtained with formazan dye image in element W.
  • R is hydrogen, alkyl or where R is alkylene and X is aliphatic acyl or cyano and R is alkyl, cycloalkyl, aryl or where R and X are as defined, provided that one and only one of R and R is always 2.
  • said binder comprises gelatin containing in the range of from about 1% to about 85% of said terpolymer.
  • R is hydrogen or methyl and R is alkyl
  • R is hydrogen or alkyl
  • 'R has its valence bonds on diiferent carbon atoms and is a divalent hydrocarbon radical or a divalent aliphatic hydrocarbon radical in which a chain of carbon atoms joining the oxygen and sulfur atoms of the above formula is interrupted by an oxygen or sulfur atom and M is a cation, and (C) about 2 to about 20%, by weight, of a monomer (3) having the formula:
  • R is hydrogen, alkyl or where R; is alkylene and X is aliphatic acyl or cyano; and R is alkyl, cycloalkyl, aryl or 0 -R 0- OHzX where R is alkylene and X is aliphatic acyl or cyano, provided that one and only one of R and R is always 0 RsO -CH2X said binder comprises gelatin containing in the range of from about 1% to about of said terpolymer.
  • R is hydrogen or methyl and -'R is alkyl
  • B about 3 to about 30%, by weight, of acrylic acid or a monomer (2) having the formula:
  • 0 oH2 ( 3-i J-0R s0zM R2 where R is hydrogen or alkyl, R has its valence bonds on different carbon atoms and is a divalent hydrocarbon radical or a divalent aliphatic hydrocarbon radical in which a chain of carbon atoms joining the oxygen and sulfur atoms of the above formula is interrupted by an oxygen or sulfur atom and M is a cation, and (C) about 2 to about 20%, by weight, of a monomer (3) having the formula:
  • R is hydrogen, alkyl or 0 Re-O CH2X where R is alkylene and X is aliphatic acyl or cyano; and R is alkyl, cycloalkyl, aryl or 0 RaO-- -CHz where R is alkylene and X is aliphatic acyl or cyano, pro vided that one and only one of R and R is always 0 R O-( l-CH2X said binder comprises gelatin containing in the range of from about 1% to about 85% of said terpolymer.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US31352A 1970-04-23 1970-04-23 Process for forming dye images Expired - Lifetime US3671244A (en)

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US3135270A 1970-04-23 1970-04-23

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US (1) US3671244A (fr)
BE (1) BE766152A (fr)
CA (1) CA954365A (fr)
FR (1) FR2090533A5 (fr)
GB (1) GB1340789A (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4268620A (en) * 1977-01-31 1981-05-19 Konishiroku Photo Industry Co., Ltd. Method of processing of light-sensitive silver halide photographic material
US4284704A (en) * 1976-08-13 1981-08-18 Eastman Kodak Company Photographic elements with incorporated hydrogen source photoreductant and tetrazolium salt
US4987177A (en) * 1989-07-18 1991-01-22 E. I. Du Pont De Nemours And Company Coating composition of an acrylic polymer containing glycidyl groups and acetoacetoxy groups and an amino ester acrylic polymer
US5185231A (en) * 1991-08-26 1993-02-09 Minnesota Mining And Manufacturing Company Dry silver systems with fluoran leuco dyes
US5206112A (en) * 1991-06-27 1993-04-27 Minnesota Mining And Manufacturing Company Positive imaging diffusion - transfer dry silver system
US5221581A (en) * 1990-12-18 1993-06-22 E. I. Du Pont De Nemours And Company Coating composition of a glycidyl acrylic polymer, an aminoester acrylic polymer and a polyester or a polyesterurethane
US5290848A (en) * 1990-12-18 1994-03-01 E. I. Du Pont De Nemours And Company Coating composition of a glycidyl acrylic polymer, an aminoester acrylic polymer and a polyester or a polyesterurethane

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4284704A (en) * 1976-08-13 1981-08-18 Eastman Kodak Company Photographic elements with incorporated hydrogen source photoreductant and tetrazolium salt
US4268620A (en) * 1977-01-31 1981-05-19 Konishiroku Photo Industry Co., Ltd. Method of processing of light-sensitive silver halide photographic material
US4987177A (en) * 1989-07-18 1991-01-22 E. I. Du Pont De Nemours And Company Coating composition of an acrylic polymer containing glycidyl groups and acetoacetoxy groups and an amino ester acrylic polymer
US5221581A (en) * 1990-12-18 1993-06-22 E. I. Du Pont De Nemours And Company Coating composition of a glycidyl acrylic polymer, an aminoester acrylic polymer and a polyester or a polyesterurethane
US5290848A (en) * 1990-12-18 1994-03-01 E. I. Du Pont De Nemours And Company Coating composition of a glycidyl acrylic polymer, an aminoester acrylic polymer and a polyester or a polyesterurethane
US5206112A (en) * 1991-06-27 1993-04-27 Minnesota Mining And Manufacturing Company Positive imaging diffusion - transfer dry silver system
US5278024A (en) * 1991-06-27 1994-01-11 Minnesota Mining And Manufacturing Company Positive imaging diffusion-transfer dry silver system using formazan dye
US5185231A (en) * 1991-08-26 1993-02-09 Minnesota Mining And Manufacturing Company Dry silver systems with fluoran leuco dyes

Also Published As

Publication number Publication date
BE766152A (fr) 1971-09-16
CA954365A (en) 1974-09-10
FR2090533A5 (fr) 1972-01-14
GB1340789A (en) 1974-01-30

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