US3247232A - Stabilizers and fixing agents for photographic silver halide emulsions - Google Patents

Stabilizers and fixing agents for photographic silver halide emulsions Download PDF

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US3247232A
US3247232A US79493A US7949360A US3247232A US 3247232 A US3247232 A US 3247232A US 79493 A US79493 A US 79493A US 7949360 A US7949360 A US 7949360A US 3247232 A US3247232 A US 3247232A
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fixing
solution
water
silver
zinc
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George W Luckey
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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
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing

Definitions

  • This invention relates to novel fixing agents and stabilizers for photographic silver halide emulsions and more particularly to metal salts of substituted arninomercaptans whose silver complexes are water-soluble, and compositions containing these compounds
  • Developed photographic silver halide emulsion layers must be fixed and/ or stabilized by a chemical treatment in order to produce a permanent silver image. If the residual silver halide is left in the developed emulsion layer, it will be converted to silver upon exposure to light thus obliterating the image. To avoid this, the developed emulsion layer is fixed by using a fixing agent which forms a water-solube complex which is then washed out of the emulsion layer along with the fixing agent.
  • any residual prior art fixing agent and/or silver halide complex left in the emulsion layer are very detrimental to the image stability.
  • prior art fixing agents When prior art fixing agents are left in emulsion layers, they form crystalline deposits upon drying and upon long standing tend to decompose and release sulfur or sulfur compounds which convert the silver image into silver sulfide.
  • residual silver halide complexes formed with prior art fixing agents will tend to decompose upon standing with the formation of silver sulfide which reduces the image density and changes its color.
  • An unfixed or an incompletely fixed silver image can be made more or less permanent by treatment with a stabilizing agent which forms a stable Water-soluble complex with the residual silver halide.
  • These complexes may be left in the emulsion layer, however, it is desirable to remove most or all of them from the emulsion to produce an image of optimum permanence.
  • Fixing and stabilizing agents such as the alkali or ammonium thiosulfates, ammonium thiocyanate, thiourea, thioglycolic acid, etc.
  • Compounds which stabilize an image may also be fixing agents, that is, they may convert the unexposed silver halide to a soluble salt which can be Washed from the emulsion.
  • stabilizing agents such as the alkali or ammonium thiosulfates, ammonium thiocyanate, thiourea, thioglycolic acid, etc.
  • a good stabilizing agent should have the following characteristics: (1) the silver complex formed should be relatively stable to sunlight, (2) the silver complex should be colorless, (3) the stabilizers should be odorless, nontoxic, non-deliquescent, (4-) the stabilizer that remains in the processed emulsion coating should not cause rapid bleaching of the silver image, and (5) the processed print should resist straining in an atmopshere of hydrogen sulfide.
  • the two most essential properties are 1 and 2.
  • fixing and stabilizing agents are mercaptan compounds. These compounds have desirable fixing and stabilizing properties, however, these compounds along with almost all of the organic compounds used before have the disadvantage of liberating an equivalent amount of hydrogen ion for every equivalent amount of silver ion that is fixed or stabilized. This causes the fixing composition pH to change drastically during the fixing or stabilizing process thus decreasing the efficiency of chemical hardeners and causing deterioration of the gelatin or other harmful side reactions.
  • Another object is to provide as a novel class of fixing and stabilizing agents, metal salts of aminomercaptans which form water-soluble silver complexes and which are characterized by not liberating acid in the fixing bath during use.
  • Another object is to provide a novel class of stabilizers and fixing agents for developed photographic silver halide emulsions which are characterized by not forming a precipitate in the emulsion coating or in the areas where the solution is spilled.
  • Another object is to provide a novel class of stabilizers and fixing agents which are relatively rapid acting and Whose fixing rate is not changed by large dilutions with water.
  • Another object is to provide a novel fixing and stabilizing composition containing a metal salt of a substituted aminomercaptan which forms a water-soluble silver complex.
  • Another object is to provide a processing element which incorporates the novel stabilizing and fixing agents of my invention and which is used for fixing and stabilizing developed photographic silver halide emulsion layers.
  • R is a substituted aminoalkyl group in which the alkyl group has from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, etc.; M is a divalent heavy metal such as zinc, cadminum, lead, etc.; and X is an acid anion, such as chloride, acetate, lactate, sulfate, nitrate, etc.
  • the substituents on the amino moiety of the aminoalkyl group may be a hydrogen atom, a lower alkyl group having from 1 to 3 carbon atoms such as methyl, ethyl, propyl, isopropyl, etc., such that no more than one of the substituents is a hydrogen atom, and these substituents may consist 2-diethylaminoethanethiol zinc acetate, Z-diethylaminoethanethiol cadmium acetate, Ethylaminoethanethiol zine acetate, 2-dimcthylaminoethanethiol zinc chloride,
  • RSMX compounds of my invention are prepared by heating equimolar mixtures of the mercaptan RSH and the heavy metal salt MX to a temperature of from 60 to 120 C. in water, alcohol, or
  • the metal salt can be crystallized from the solution but in others the salt is very difficult to crystallize.
  • the properties of these compounds depend upon the mercaptan and on the heavy metal salt.
  • the cadmium salts in general, are less soluble than the zinc salts and can be crystallized.
  • the zinc acetate salt of 2-morpholinoethanethiol hydrochloride can be crystallized but the zinc acetate salt of 2-ethylaminoethanethiol hydrochloride cannot be crystallized. When an aqueous solution of the latter compound is evacuated for 24 hours the solvent evaporates leaving a colorless, glassy solid with no detectable crystal structure. This failure of the zinc salts to crystallize is a very useful property.
  • the compounds of my invention are characterized by properties which make them valuable for use in stabilizers and fixers for silver halide emulsions.
  • the zinc acetate of Z-diethylaminoethanethiol hydrochloride is a colorless, glassy solid without detectable crystal structure.
  • Gelatino-silver halide emulsions that contain this salt have been stored for 3 months without any observable crystallization and solutions of this salt do not form objectionable crystalline deposits when they are spilled.
  • the zinc salt of 2-aminoethanethiol hydrochloride is a very rapid fixing agent but forms an insoluble precipitate when the silver ion concentration reaches a certain level, while the zinc salt of the diethyl compound does not form a precipitate as rapidly but also does not fix as rapidly. Consequently, equal volumes of the zinc salts of Z-aminoethanethiol hydrochloride and 2-diethylaminoethanethiol hydrochloride have been blended and used as a concentr-ated fixing bath.
  • coarse grain silver bromoiodide emulsion type medical X-ray films such as Kodak Blue Brand X-ray Film and Kodak No-Screen Medical X-ray Film can be fixed with a blended solution and washed more rapidly than when a rapid fixer with hardener is used that has the formula:
  • Aluminum chloride hexahydrate g 12.5 Water to cc 25 Combine solutions A and B and dilute with water to one liter.
  • the blend of the two zinc salts has the fading properties of Z-aminoethanethiol hydrochloride salt.
  • the proportion of diethylaminoethanethiol in the mixture is increased, the rate of clearing decreases but the fading properties are still similar to those of the 2-aminoethanethiol.
  • the silver ion concentration in the 50:50 bath increases, some precipitation occurs in the emulsion layers. This is easily removed by washing in water.
  • a silver bromoiodide emulsion type medical X-ray film such as Kodak Blue Brand X-ray Film is fixed in 40 seconds at 25 C. with a 50:50 concentrate that is diluted with 4 parts of water, in 50 seconds when the solution is diluted with 10 parts of water, in 70 seconds when diluted 15 fold, and seconds when diluted 20 fold.
  • the metal salts of substituted aminomercaptans of my invention apparently do not react with the skin in the same way that the aminomercaptans per se do, or if they do, the rate and extent of the reaction are negligible. After immersion in the solutions, the skin can be cleaned by a simple wash in soap and water and no persistent odor remains. It appears that in the preparation of these metal salts, odor producing impurities are removed from the solution perhaps as insoluble salts of the more volatile mercaptans.
  • My compounds are characterized by having very low dissociation in water solution.
  • the zinc acetate salt of Z-aminoethanethiol hydrochloride has an equilibrium dissociation of about 10 Because of the very low dissociation of these compounds, the discovery that the formation of the metal salt complex such as the zinc or the cadmium complex has relatively little effect on the rate of fixation was unexpected. Apparently the rate of dissociation of the complex is very rapid when compared with the rate of fixation.
  • Concentrated hardening fixing baths have been prepared by mixing the zinc salt of diethylaminoethanethiol' hydrochloride with glutaraldehyde or 'succinaldehyde. This is a unique property of metal salts; if the mercaptoamine is mixed with the glutaraldehyde or succinaldehyde, mercaptals form and the fixing and hardening rates decrease. Hardening fixing baths containing mercaptals of glutaraldehyde and succinaldehyde release acid during' the fixing process which reduces their stability. When the zinc salts are used, there is no decrease in either fixing or hardening action even when the salts are stored for 3 months at room temperatures.
  • Hardening fixing baths have also been made by adding aluminum compounds to metal salt fixing baths. However, these do precipitate in emulsions when they are not washed out and the concentration that can be achieved is not nearly as good as that of the glutaraldehyde baths.
  • the compounds of my invention can be used in mono baths, solvent transfer, and in other applications where sodium thiosulfate or analogous silver halide solvents are now used.
  • the preferred metal salts of substituted aminomercaptans of my invention have at least one alkyl substituent on the amino group.
  • the zinc acetate salt of di ethylaminoethanethiol hydrochloride yields a more stable image than the corresponding aminoethanethiol salt.
  • compositions containing them include solutions in which developed silver halide emulsion layers are fixed and/or stabilized, and also processing elements or webs incorporating the compounds of my invention which are squeegeed against the developed silver halide emulsion layer and then stripped off after the silver image has been fixed and/ or stabilized.
  • Example 1 Sixty-eight grams of diethylaminoethanethiol hydrochloride were dissolved in 18 grams of water and heated to 60 C. Eighty-four grams of zinc acetate dihydrate were added to the warm solution, and the mixture heated with stirring to 110 C. The volume of the solution after filtration was 120 ml. and the total weight was 156 grams. When one part of this solution was diluted with 9 parts of water by volume, the resulting solution had a pH of 4.4. When the solution was diluted with three parts of water, it cleared a 50 micron thick coating of nuclear track emulsion in 16 minutes at 23 C. The coating was dried without washing and stored for three months at room temperature. During this tnne, no crystallization or yellowing of the thick coating occurred.
  • Example 2 A stabilizing bath was prepared by mixing equimolar quantities of zinc acetate and diethylaminoethanethiol as in Example 1. The concentrated solution was diluted with 4 volumes of water and enough glutaraldehyde was added to yield a concentration of 25 grams per liter. This solution cleared wet low contrast, coarse grain silver 6 bromoiodide emulsion film such as Kodak Matrix Film in 60 seconds at 23 C. and the processed emulsion did not soften or reticulate when immersed in water at 45 C. Wet Kodak Blue Brand Medical X-ray Film cleared in seconds at 23 C.
  • the pH of the dilute solution was 4.5, and this did'not change when 160 8 x 10 inch sheets of the unexposed X-ray film were processed in one gallon of the solution.
  • the hardening properties were unaffected by this exhaustion, but the clearing time in creased from 90 seconds to seconds.
  • the properties of this solution were unchanged after storage for 3 months at room temperature.
  • a fixer with hardener bath having Formula A cleared the X-ray film in about 2() seconds under these conditions, but again, additional fixing time and washing were needed to prevent crystallization.
  • the clearing time increased to about 30 seconds when 160 8 x 10 inch sheets of fiim were processed in one gallon of the solution.
  • the over-all time for processing X-ray film was comparable with that of the zinc salt bath.
  • the fading of silver images was tested with a paper support coated with a silver chlorobromide printout emulsion such as Kodak Linagraph Direct Print Paper. Since printout images are composed of very finely divided silver, they are particularly susceptible to fading. Samples of exposed print paper were bathed in a solution having the Formula A with and without 10 grams of silver nitrate per liter and in the zinc salt bath. The printout images that were processed in the hypo bath faded within 10 minutes when no silver ion was present in the solution. If silver ion was present, the images faded somewhat and the background areas became brown. The images also had a warm tone. The image that was fixed in the zinc salt bath did not fade appreciably and the background areas had a cream color, even after storage for two and one-half months at room temperautrc.
  • Example 3 The zinc acetate and cadmium acetate salts of 2-diethylaminoethanethiol and 2-morpholinoethanethiol hydrochlorides were prepared by heating equal molar quantities in aqueous solution as described in Example 1.
  • the Zinc salt of the morpholino compound formed a clear colorless solution, the cadmium salt had a pale yellow color.
  • These solutions were diluted to five times their volume with water and used to stabilize Kodak Linagraph Direct Print Paper. The images stabilized in this way were stable for one week at 50 C. and 100 percent RH. while a similar image stabilized with a fixing bath with Formula C faded completely.
  • the solution of the zinc salt of 2-morpholinoethanethiol hydrochloride crystallized when it was dried, and gelatin coatings made from a water solution that contained 30 percent morpholinoethanethiol zinc acetate and 7 percent gelatin, also crystallized when dried.
  • the zinc chloride salt of morpholinoethanethiol cleared wet medical X-ray film in 70 seconds at 25 C. when its concentration was between 100 and 400 grams per liter. This salt was a white crystalline compound, readily soluble in water.
  • the solution that contained 100 grams per liter had a pH of 4.1.
  • Example 4 The zinc acetate salt of Z-aminoethanethiol hydrochloride was prepared by heating 90.8 grams of the thiol with 87.8 grams of zinc acetate dihydrate in 50 ml. of ethanol, to a temperature of 115 C. The final weight of the solution after heating was 164 grams. This concentrate was diluted so that the dilute solution contained the equivalent of 226 grams per liter of mercaptan. This dilute solution cleared wet Kodak Blue Brand Medical X-ray Film in 20 seconds and wet Kodak No-Screen X-ray Film in 150 seconds at 26 C.
  • Example 5 The zinc acetate salts of 2-aminoethanethiol hydrochloride and 2-diethylaminoethanethiol hydrochloride were prepared as described in Examples 1 and 4. The concentrated solutions were then mixed to form blends that contained 0, 25, 50, 75, and 100 percent of the zinc acetate salt of the diethylaminoethanethiol hydrochloride (Zindeaet) by volume. One part of each blend was diluted with four parts of water to form working solutions which were used to fix Kodak No-Screen Medical X-ray Film. The tunes to clear this film are summarized in the table below:
  • Example 7 A stabilizing bath was prepared by mixing 2.115 grams of ethylaminoethanethiol hydrochloride with 10 m1. of water at 50 C. Then 3.29 grams of zinc acetate dihydrate were added and the solution heated to 60 C. The volume of the solution was increased to 25 ml. and evacuated with a Water pump for 10 minutes. The solution was cooled and the pH adjusted to 3.5. This bath cleared wet Kodak Blue Brand Medical X-ray Film in 55 seconds at 25 C., and cleared an industrial X-ray film with a coarse grain silver bromoiodide emulsion such as Kodak No-Screen Industrial X-ray Film in 5 minutes and 30 seconds at the same temperature.
  • Example 8 A stabilizing bath was prepared by mixing 4.45 grams of 2-mercapto-3-morpholinopropanol, 3.43 grams of zinc chloride and 25 ml. of methanol. The mixture was heated until the zinc chloride dissolved, then water was added to increase the volume to 25 ml. This stock solution was mixed with additional water to make a solution which contained 0.6 mole of sulfur per liter. At a pH of 4.0, the 0.6 m. solution cleared Kodak Blue Brand Medical X-ray Film in seconds at 25 C.
  • Example 9 A stabilizing bath was prepared by mixing 4.25 grams of Z-dimethylaminoethanethiol hydrochloride with 4.09 grams of zinc chloride and 85 grams of water. Sodium carbonate was added to maintain the pH between 5 and 6 while heating the mixture to 70 C. After cooling to 20 C., the pH was decreased to 3.5 with hydrochloric acid. At 20 C., this solution cleared 'wet Kodak Blue Brand Medical X-ray Film in 150 seconds.
  • Example 10 A stabilizing bath was prepared by mixing 2.96 grams of di-isopropylaminoethanethiol hydrochloride with 3.25 grams of zinc acetate dihydrate and 15 ml. of water. This mixture was heated to C. and kept at this temperature for 10 minutes followed by exacuation with a water pump for 30 minutes as the solution cooled. The volume was then increased to 25 ml. with water and the pH was adjusted to 3.5 with hydrochloric acid. This solution cleared wet Kodak Blue Brand Medical X-ray Film in seconds at 25 C.
  • Example 11 A stabilizing bath was prepared by mixing 18.9 grams of lead acetate, 8.5 grams of diethylaminoethanethiol 9 hydrochloride and 5 grams of water. The mixture was heated to 70 C. until the lead acetate dissolved. The viscous liquid was then diluted to 100ml. with water. The pH of this diluted solution was 4.2. At a temperature of 75 F., this solution cleared Kodak Blue Brand Medical X-ray Film in 120 seconds.
  • Example 12 A stabilizing bath was prepared by mixing 2.96 grams of di-n-propylaminoethanethiol hydrochloride with 3.29 grams of zinc acetate dihydrate and 15 ml. of water. This mixture was heated to 105 C. and kept at this temperature for minutes followed by evacuation with a water pump for 30 minutes as the solution cooled. The volume was then increased to 25 ml. with Water and the pH was adiusted to 3.5 with hydrochloric acid. This solution cleared Wet Kodak Blue Brand Medical X-ray Film in 320 seconds at 25 C.
  • Example 13 The extreme compatibility of the zinc salt fixing bath with gelatin was studied by making gelatin coatings. Seven grams of bone gelatin was dissolved in 100- ml. of an aqueous solution that contained 30 grams of zinc acetate salt of diethylaminoethanethiol hydrochloride. The zinc salt was prepared by dissolving equal molar amounts of diethylaminoethanethiol hydrochloride and zinc acetate in isopropanol and heating. A small amount of water was added to accelerate the reaction. After drying, the zinc acetate salt was added to water to make the solution.
  • the gelatin solution of the zinc salt was coated at a wet thickness of 0.003 inch on 0.003 inch thick acetate butyrate support and also coated on 0.0015 inch support.
  • the coatings dried without crystallization and no curl was observed even after storage for one month.
  • large amounts of the zinc salt can be retained by a gelatin coating without damage to its physical properties.
  • These fixing sheet coatings contain more than enough fixing agents to clear one side of Kodak Blue Brand Medical X-ray Film.
  • Example 14 A processing element for stabilizing a silver image was prepared by coating a transparent support with a 0.003 inch thick coating of a coating melt having the composition:
  • An exposed silver halide emulsion layer was developed in a conventional photographic developer and immediately laminated to a sample of the above-described stabilizing sheet. Room lights were turned on in 15 seconds with no visible effect on the image in the photographic emulsion. Extended keeping of this stabilized image showed no further action of light on the photographic emulsion and no developer stain.
  • Another sample of the developed silver halide emulsion layer was stabilized by bringing a hardened gel stabilizing pad into contact with it for a short time and then re moving the pad leaving the processed emulsion layer with a silver image that was stable to roomlight exposure and free of developer stain.
  • metal salts of my aminomercaptans can be incorporated in layers of a hydrophilic material such as gelatin, polyvinyl alcohol, polyvinyl butal, polyvinyl acetate, ethyl cellulose, methyl cellulose, copolymers of acrylic acid and acrylonitrile, such as are disclosed in Calvier et al., US. Serial No. 541,547, filed October 19, 1955, now US. Patent 2,968,558, issued January 17, 1961 etc., to make fixing and stabilizing pads or webs according to my invention.
  • Some zinc salts of my invention are particularly well suited for incorporation in pads or webs used for fixing and/or stabilizing photographic images since these salts do not crystallize.
  • the support for a stabilizing pad that is to be laminated to a developed photographic element may be a thin layer of any material that is transparent, colorless, permeable to water but preferably not permeable to the metal salts of my invention.
  • the supports used for fixing and stabilizing pads or webs that are held in contact with the developed photographic layer for the fixing and stabilizing step and then separated from the completely processed layer may be any of those that are satisfactory for the lamination type of pad, however, this support can be opaque and need not be water-permeable.
  • the .aminomercaptan hydrochlorides used in making my metal salts may be made in a manner similar to that used by Gabriel, Ber. 22, 1137 (1889) abstracted by Chem. Abstracts 31, 1362 if they are not readily available commercially.
  • the preferred metal salts of substituted aminomercaptans form water-soluble silver complexes, however, it is possible to make such salts that will form water-insoluble silver complexes.
  • novel metal salts of aminomercaptans of my invention are valuable agents for fixing and/ or stabilizing the silver image in a developed silver halide emulsion layer. They are characterized by being relatively rapid acting fixing and stabilizing agents. They have the valuable advantage over prior art organic fixing and stabilizing agents of not releasing an equivalent amount of hydrogen ions for every equivalent amount of silver ion fixed as do the prior art agents. Thus my fixing and/ or stabilizing compositions do not loose their effectiveness because of a decrease in pH during use as do prior art compositions. Because of this, my compositions may be used to treat larger amounts of a given kind of film than is possible with prior art compositions before becoming exhausted.
  • My agents are characterized by not forming mercaptals with the hardening agents glutaraldehyde and succinaldehyde when used with them in a hardening fixing bath.
  • Prior art agents such as the aminomercaptans when used in such hardening fixing baths form mercaptals which become ineffective as hardening agents when sufiicient acid has been released by fixation so that the hardening reaction is inhibited.
  • Compositions containing my metal salts of aminomercaptans may be readily washed from the users hands without leaving the strong, unpleasant odor characteristic of prior art mercaptans. Some of my compositions do not crystallize upon drying and therefore photographic elements treated with them can be dried without washing and yet be free of crystalline deposits.
  • my zinc salts are particularly valuable for incorporating in the hydrophilic layers of fixing and/or stabilizing pads that are superior to prior art pads. Since the silver complexes of my salts are transparent and colorless when left in emulsion coatings, the stabilizing pad can be laminated to the developed photographic emulsion layer.
  • R represents an N-substituted aminoalkyl group selected from the class consisting of an N-alkyl'amino- ,alkyl group, a N,N-dialkyl'aminoalky1 group and an N- morpholinoalkyl group, in which the alkyl'moiety has from 1 to 4 carbon atoms and the alkylmoiety has from 1 to 3 carbon atoms;
  • M is a metal selected from the class consisting of zinc, cadmium and lead; and
  • X is an acid anion.

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  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US79493A 1960-12-30 1960-12-30 Stabilizers and fixing agents for photographic silver halide emulsions Expired - Lifetime US3247232A (en)

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GB1009085D GB1009085A (enrdf_load_stackoverflow) 1960-12-30
US79493A US3247232A (en) 1960-12-30 1960-12-30 Stabilizers and fixing agents for photographic silver halide emulsions
FR883469A FR1312687A (fr) 1960-12-30 1961-12-29 Sel métallique complexe d'aminomercaptan et fixateur et stabilisant photographiques e contenant

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617289A (en) * 1966-12-10 1971-11-02 Fuji Photo Film Co Ltd Stabilization process for thermally developable light-sensitive elements

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1440962A (en) * 1922-04-01 1923-01-02 Naugatuck Chem Co Process for vulcanizing rubber and products obtained thereby
US2696439A (en) * 1952-01-04 1954-12-07 Levinos Steven Photographic stabilization process
US2805233A (en) * 1953-11-23 1957-09-03 Jefferson Chem Co Inc Metal phenolates and process of producing same
US2871121A (en) * 1955-12-14 1959-01-27 Kimura Shuji Photographic fixer-hardener compositions
US2885416A (en) * 1955-04-01 1959-05-05 Montedison Spa Process of preparing zinc containing fungicides
US2983726A (en) * 1959-08-18 1961-05-09 Goodrich Co B F Method for preparing secondary aminothiazoledisulfides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1440962A (en) * 1922-04-01 1923-01-02 Naugatuck Chem Co Process for vulcanizing rubber and products obtained thereby
US2696439A (en) * 1952-01-04 1954-12-07 Levinos Steven Photographic stabilization process
US2805233A (en) * 1953-11-23 1957-09-03 Jefferson Chem Co Inc Metal phenolates and process of producing same
US2885416A (en) * 1955-04-01 1959-05-05 Montedison Spa Process of preparing zinc containing fungicides
US2871121A (en) * 1955-12-14 1959-01-27 Kimura Shuji Photographic fixer-hardener compositions
US2983726A (en) * 1959-08-18 1961-05-09 Goodrich Co B F Method for preparing secondary aminothiazoledisulfides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617289A (en) * 1966-12-10 1971-11-02 Fuji Photo Film Co Ltd Stabilization process for thermally developable light-sensitive elements

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