US2835581A - Tetrazaindenes and photographic emulsions containing them - Google Patents

Tetrazaindenes and photographic emulsions containing them Download PDF

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Publication number
US2835581A
US2835581A US515785A US51578555A US2835581A US 2835581 A US2835581 A US 2835581A US 515785 A US515785 A US 515785A US 51578555 A US51578555 A US 51578555A US 2835581 A US2835581 A US 2835581A
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emulsions
emulsion
photographic
fog
methyl
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John F Tinker
Jr John Sagal
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to GB18232/56A priority patent/GB814823A/en
Priority to FR1158160D priority patent/FR1158160A/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/14—Nitrogen atoms
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression

Definitions

  • This invention relates to fog inhibiting agents and stabilizers for photographic emulsions and to photographic emulsions containing them.
  • Fog depends both on the emulsion and the conditions of development; for a given emulsion it increases with the degree of development. With constant development conditions, it tends to increase with time, temperature and relative humidity of storage conditions; it is common practice to make accelerated tests of the stability of photographic emulsions by storage at increased temperature or humidity, or both. It is, of course, desirable to have emulsions as stable as possible under the conditions of high temperature and humidity which may occur in tropical climates, for example. Fog usually appears over the whole area of the sensitive coating, but when severe, it frequently is non-uniform. Fog may also be caused by exposure to chemicals, for example, hydrogen sulfide and other reactive sulfur compounds, hydrogen peroxide vapor, and strongly reducing materials. While antifoggants and stabilizers may protect, to some extent, against such effects, it is normally understood that an antifoggant protects against spontaneous growth of fog during prolonged storage or storage at high temperatures and humidities, or during development to maximum contrast and speed, or both.
  • an object of the present invention to provide a method for stabilizing photographic emulsions.
  • a further object is to provide a means for reducing the fog produced upon keeping of such emulsions which have r been sensitized, especially emulsions stored under tropical or other adverse conditions.
  • a still further object is to provide a means for stabilizing the speed and contrast of sensitized photographic emulsions.
  • R2 N N atent and R represents a hydrogen atom, an alkyl group (such as methyl, ethyl, etc.), or an aryl group (such as phenyl, tolyl, etc., especially a mononuclear aromatic group of the benzene series).
  • R represents a methyl group and R represents a hydrogen atom have been found to be especially useful in practicing our invention.
  • the compounds selected from those represented 1 by Formula I above can advantageously be prepared by condensing 3-amino-5-hydroxy-methyl- 1,2,4-triazole together with an ester selected from those represented by the following general formula: (II) (I) R2 R1- CHCOORa wherein R and R each has the values given above'and R represents a lower alkyl group (such as methyl, ethyl, etc).
  • R and R each has the values given above'and R represents a lower alkyl group (such as methyl, ethyl, etc).
  • the compounds selected [from those represented by Formula I above wherein R is a halogen atom can advantageously be prepared by heating together a compound selected from those represented by Formula I above wherein R is a hydroxyl group and a phosphoryl halide, such as phosphoryl chloride. Illustrative examples of these methods are given below.
  • the antifoggant compounds represented by Formula I can be employed in emulsions which have been sensitized optically or chemically, or emulsions which have not been so sensitized. It is known that the efiective sensitivity of photographic silver halide emulsions can be increased by adding to them derivatives of alkylene oxides, such as ethylene oxide polymers having molecular weights of 300 or more. The practical value of these compounds is severely limited by their tendency to increase fog on storage of the photographic film, especially storage at elevated temperatures and humidity. It has been found difiicult to control this by the antifoggants commonly available without using quantities of antifoggants which partly neutralize the speed increase obtained from the alkylene oxide derivatives.
  • the alkylene oxide polymers used to sensitize the emulsions can be of various types.
  • the alkylene oxides from which the polymers are derived contain from 2 to 4 carbon atoms, e. g., ethylene oxide, propylene oxide and butylene oxide.
  • the preparation of polymers from these compounds is described in Ellis, The Chemistry of Synthetic Resins (1935), pages 990 to 994.
  • These compounds are also referred to as polyalkylene glycols and their use as sensitizers for silver halide emulsions is described in U. S. Patents 2,423,549 and 2,441,389.
  • Ethylene oxide polymers have been found to be especially advantageous in practicing our invention.
  • alkylene oxides may also be used to sensitize the silver halide emulsions, e. g., condensation products of alkylene oxide with glycols, such as those having from 8 to 18 carbon atoms, as described in U. S. Patent 2,240,472 and British Patent 443,559, as well as condensation products of alkylene oxides with aliphatic alcohols, aliphatic acids and aliphatic amines, that is, polyalkylene ethers, esters and amides, the preparation of which is described in U. S. Patent 1,970,- 578, condensation products of alkylene oxides with phenols, also described in U. S. Patent 1,970,578, and condensation products of alkylene oxides with hexitol ring dehydration products, as described in U. S. Patent 2,400,532.
  • condensation products of alkylene oxide with glycols such as those having from 8 to 18 carbon atoms, as described in U. S. Patent 2,240,472 and British Patent 44
  • polyalkylene oxide or derivative of alkylene oxide should have a molecular weight of at least 300.
  • Condensation products of ethylene oxide with long chain alcohols should have a molecular weight of about 700; other derivatives may have a molecular weight of 1500 to 4000 or more.
  • the principal purpose of our invention is to provide a means for maintaining the sensitivity and fog of silver halide emulsions at or close to initial optimum values under conditions of high temperature or high humidity, or both.
  • the antifoggants of our invention are added to the emulsion at any stage during the process of manufacture prior to coating the emulsion.
  • the antifoggants can be added to the emulsion in solution in water or any convenient solvent not injurious to the emulsion, such as lower aliphatic alcohols.
  • antifoggants which we employ when added in suitable concentration before coating to unsensitized or optically sensitized silver halide emulsions usually do not appreciably affect the sensitivity and fog when measurements are made soon after coating. However, when sensitometric measurements are made after appreciable intervals of time under tropical or dry conditions of storage at elevated temperatures, the antifoggants do stabilize speed and maintain fog at a low level.
  • alkylene oxide derivatives which can be used to sensitize the emulsions can be illustrated by the following specific examples, although our invention is in no way limited to the use of these specific compounds.
  • the preparation of silver halide emulsions involves three separate operations: (1) the emulsification and digestion or ripening of the silver halide, (2) the freeing of the emulsion from aqueous soluble salts usually by washing, (3) the second digestion or after-ripening to obtain increased sensitivity (Mees, The Theory of the Photographic Process, 1942, page 3).
  • the fog inhibiting agents can be added at any stage, preferably after the final digestion.
  • the photographic emulsions which we use are of the developing-out type and best results have been obtained with gelatino-silver bromoiodide emulsions. However, emulsions of varying halide content can be used.
  • the emulsions can be chemically sensitized by any of the accepted procedures.
  • the emulsions can be digested with naturally active gelatin, or sulfur compounds may be added such as those described in Sheppard U. S. Patent 1,574,944 and U. S. 1,623,499, and Sheppard and Brigham U. S. Patent 2,410,689.
  • the emulsions can also be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium and platinum, all of which belong to group VIII of the periodic table of elements and have an atomic weight greater than 100.
  • Representative compounds are ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U. S. Patent 2,448,060, and as antifoggants in higher amounts, as described in Trivelli and Smith U. S. Patents 2,566,245 and 2,566,263.
  • the emulsions can also be chemically sensitized with gold salts as described in Waller and Dodd U. S. Patent 2,399,083, or stabilized with gold salts as described in Damschroder U. S. Patent 2,597,856 and Yutzy and Leermakers U. S. Patent 2,597,915.
  • Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2- aurosulfobenzothiazole methochloride.
  • the emulsions can also be chemically sensitized with reducing agents, such as stannous salts (Carroll U. S. Patent 2,487,850), polyamines such as diethylene triamine (Lowe and Jones U. S. Patent 2,518,698), polyamines such as spermine (Lowe and Allan U. S. Patent 2,521,925), or bis-([i-aminoethyl) sulfide and its water-soluble salts (Lowe and Jones U. S. Patent 2,521,926).
  • reducing agents such as stannous salts (Carroll U. S. Patent 2,487,850), polyamines such as diethylene triamine (Lowe and Jones U. S. Patent 2,518,698), polyamines such as spermine (Lowe and Allan U. S. Patent 2,521,925), or bis-([i-aminoethyl) sulfide and its water-soluble salts (Lowe and Jones U. S. Patent 2,521,
  • the emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray U. S. application Serial No. 319,611 (now U. S. Patent 2,728,663, issued December 27, 1955); Carroll and Murray U. S. application Serial No. 319,612 (now U. S. Patent 2,728,664, issued December 27, 1955); and Leubner and Murray U. S. application Serial No. 319,613 (now U. S. Patent 2,728,665, issued December 27, 1955), all filed November 8, 1952.
  • the antifoggants of our invention alone, or in combination with polyalkylene oxides or their derivatives, are. effective in the presence or absence of optical sensitizing dyes. Since optical sensitizing can affect stability of emulsions with respect to sensitivity, fog and latent image changes, the action of the antifoggants is not completely independent of optical sensitizing or other emulsion variables. We have found, however, that both unsensitized emulsions and emulsions sensitized with cyanine or merocyanine dyes, or both, can be treated with the antifoggant compounds represented by Formula I above.
  • the quantity of antifoggaut compound employed can In a manner similar to that illustrated in the above examples, other compounds selected from those represented by Formula I .can be used to stabilize photographic silver halide emulsions, either in the presence or abbe varied, depending upon the particular silver halide 5 sence of chemical sensitizers. employed, degree of ripening, presence or absence of We have also found that compounds corresponding to other emulsion addenda, etc.
  • the quantity of those of Formula I wherein R represents a formamidinoantifoggant mu vary from about 0.1 to 10 grams per thio (hydrochloride) group can be employed in photogram mole of silver halide in the emulsion.
  • graph1c silver halide emulsions though less advantageousamounts can be used in combination with one or more 10 ly than the compounds represented by Formula I. of the chemical sensitizing and stabilizing agents listed Instead of incorporating the antifoggants in the photoabove.
  • graphic silver halide emulsion these antifoggants can be The stabilizing action alforded by the antifoggants of incorporated 1n a colloid layer, such as a gelatin overour invention was determined by incubation of the coating layer or inter'layer, in contact with the emulsion. emulsions for a period of two weeks at 120 F. and at The fog-inhibiting agents which we have described can constant humidity.
  • the speeds were measured in terms be used in various kinds of photographic emulsions. In of 30/E where E is die exposure required to produce a addition to being useful in non-sensitrzed emulsions, they density of 0.2 above fog.
  • the antifoggants were added can also be used in orthochromatic, panchromatic, and to a panchromatically sensitized, high speed silver bromi- X-ray emulsions. If used with sensitizing dyes they can odide emulsion which had been chemically sensitized with be added to the emulsion before or after the dyes are a sulfur compound, such as described in Sheppard U. S. added.
  • Various silver halides can be used as the light- Patent 1,574,944 and potassium chloroaurate.
  • the emulsensitive material, lncludmg silver bromide, silver iodide, sions were coated on a cellulose acetate support and the silver chloride, silver bromiodide, silver chlorobromide, coatings exposed on an Eastman I(b) Sensitometer silver chlorobromiodide, etc.
  • the antifoggants of our and processed for four minutes in a developer can be used in emulsions intended for color D-19.
  • a developer having the following composition: photography, for example, emulsions containing colora forming couplers, or emulsions to be developed by solu- Water about 500 tions containing couplers.
  • N'ntethyl'p'ammopilenol sulfate The polyethylene oxide polymers used in th emulsiqns deslccated "5-- according to our invention can be prepared either 'by fiydyoqmnone p g polymerizing ethylene oxide in the presence of aliphatic Sodlm? a 'monchydmte "jg-- acids, aliphatic amines, or phenols, or by reacting the poly- Potasslum brom'de g merized polyethylene oxide with aliphatic acids, acid Cold Water to make one hterchlorides, or esters,.whic;h produces similar products.
  • the exposed coatings werepuocessed for The dlspersm? agents b5 gelatin or i colloids five minutes in Kodak D1950 developer hafing the such as collodion, albumen, cellulose derivatives, synlowing composition. thetie resins, etc.
  • Example 10 -2-formamidinothi0methyl-4-hydr0xy-6- methyl-1,3,3a,7-tetrazaindene Two grams of 2-chloromethyl-4-hydroxy-6-methyltetrazaindene and one gram of thiourea in 100 cc. of ethanol were refluxed 8 hours. Three hundred cc. more alcohol were added, heated to boiling, and filtered. The residue recrystallized from 70 cc. of aqueous ethanol, yielding 0.6 gram, M. P. 262-264 C. dec.
  • Example 13 is(2 formamidirwthiomethyl-6-methyl- 1,3,3a,7-tetrazainden-4-yl)-sulfide dihydrochloride dihydrate
  • R represents a member selected from the group consisting of a hydroxyl group and a chlorine atom
  • R represents a member selected from the group consisting of a methyl group and a mononuclear aromatic group of the benzene series
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 2 carbon atoms, and a mononuclear aromatic group of the benzene series.
  • R represents a member selected from the group consisting of a hydroxyl group and a chlorine atom and R represents a member selected from the group consisting of a hydrogen atom, and alkyl group containing from 1 to 2 carbon atoms, and a mononuclear aromatic group of the benzene series.

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US515785A 1955-06-15 1955-06-15 Tetrazaindenes and photographic emulsions containing them Expired - Lifetime US2835581A (en)

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US515785A US2835581A (en) 1955-06-15 1955-06-15 Tetrazaindenes and photographic emulsions containing them
GB18232/56A GB814823A (en) 1955-06-15 1956-06-13 Improved antifogging and stabilising agents for photographic silver halide emulsion
FR1158160D FR1158160A (fr) 1955-06-15 1956-06-15 Nouveaux composés de la série du tétraazaindène et leurs applications en photographie

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3053657A (en) * 1959-05-04 1962-09-11 Eastman Kodak Co Photographic silver halide diffusion transfer process
DE1155333B (de) * 1961-03-27 1963-10-03 Eastman Kodak Co Photographisches Material fuer die Herstellung von mehrfarbigen Bildern nach einem Farbstoffentwicklersubstanzen verwendenden Diffusionsuebertragungsverfahren und Durchfuehrung des Verfahrens
US4078937A (en) * 1974-11-26 1978-03-14 Fuji Photo Film Co., Ltd. Process for sensitizing a fine grain silver halide photographic emulsion
US4302525A (en) * 1978-06-26 1981-11-24 Polaroid Corporation Novel photosensitive elements and method of stabilizing said elements
US4332888A (en) * 1978-11-20 1982-06-01 Polaroid Corporation Method for stabilizing and spectrally sensitizing photosensitive silver halide emulsion
EP0185243A2 (en) 1984-12-17 1986-06-25 Minnesota Mining And Manufacturing Company Photosensitive silver halide material for obtaining half-tone black-and-white images and method for half-tone high-contrast reproduction
US4610958A (en) * 1983-12-07 1986-09-09 Konishiroku Photo Industry Co., Ltd. Process of preparing a silver halide emulsion
EP0171238A3 (en) * 1984-07-28 1988-03-30 Konishiroku Photo Industry Co. Ltd. Silver halide grains, preparation thereof and light-sensitive photographic material containing said grains
US4863843A (en) * 1984-10-30 1989-09-05 Mitsubishi Paper Mills, Ltd. Silver halide photographic emulsion containing predominantly silver bromide
US4888273A (en) * 1988-02-26 1989-12-19 Polaroid Corporation Stabilized tabular silver halide grain emulsions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2407204A (en) * 1944-07-22 1946-09-03 American Cyanamid Co Triazolo (d) pyrimidines and methods of preparing the same
US2449225A (en) * 1946-10-22 1948-09-14 Gen Aniline & Film Corp 7-amino and 7-hydroxy-1, 3, 4-triazaindolizines as stabilizers for photographic silver-halide emulsions
US2519715A (en) * 1947-11-12 1950-08-22 American Cyanamid Co 1-carbamyl-4-heterocyclopiperazines
US2657136A (en) * 1951-03-30 1953-10-27 Eastman Kodak Co Photographic antiplumming agents and compositions containing them
US2673152A (en) * 1953-02-16 1954-03-23 Eastman Kodak Co Azopyridine compounds as fog inhibitors for photographic emulsions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2407204A (en) * 1944-07-22 1946-09-03 American Cyanamid Co Triazolo (d) pyrimidines and methods of preparing the same
US2449225A (en) * 1946-10-22 1948-09-14 Gen Aniline & Film Corp 7-amino and 7-hydroxy-1, 3, 4-triazaindolizines as stabilizers for photographic silver-halide emulsions
US2519715A (en) * 1947-11-12 1950-08-22 American Cyanamid Co 1-carbamyl-4-heterocyclopiperazines
US2657136A (en) * 1951-03-30 1953-10-27 Eastman Kodak Co Photographic antiplumming agents and compositions containing them
US2673152A (en) * 1953-02-16 1954-03-23 Eastman Kodak Co Azopyridine compounds as fog inhibitors for photographic emulsions

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3053657A (en) * 1959-05-04 1962-09-11 Eastman Kodak Co Photographic silver halide diffusion transfer process
DE1155333B (de) * 1961-03-27 1963-10-03 Eastman Kodak Co Photographisches Material fuer die Herstellung von mehrfarbigen Bildern nach einem Farbstoffentwicklersubstanzen verwendenden Diffusionsuebertragungsverfahren und Durchfuehrung des Verfahrens
US3161506A (en) * 1961-03-27 1964-12-15 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers
US4078937A (en) * 1974-11-26 1978-03-14 Fuji Photo Film Co., Ltd. Process for sensitizing a fine grain silver halide photographic emulsion
US4302525A (en) * 1978-06-26 1981-11-24 Polaroid Corporation Novel photosensitive elements and method of stabilizing said elements
US4332888A (en) * 1978-11-20 1982-06-01 Polaroid Corporation Method for stabilizing and spectrally sensitizing photosensitive silver halide emulsion
EP0145440A3 (en) * 1983-12-07 1987-09-02 Konishiroku Photo Industry Co. Ltd. Process of preparing a silver halide emulsion
US4610958A (en) * 1983-12-07 1986-09-09 Konishiroku Photo Industry Co., Ltd. Process of preparing a silver halide emulsion
EP0171238A3 (en) * 1984-07-28 1988-03-30 Konishiroku Photo Industry Co. Ltd. Silver halide grains, preparation thereof and light-sensitive photographic material containing said grains
US4917996A (en) * 1984-07-28 1990-04-17 Konishiroku Photo Industry Co., Ltd. Silver halide grains, preparation thereof and light-sensitive photographic material containing said grains
US4863843A (en) * 1984-10-30 1989-09-05 Mitsubishi Paper Mills, Ltd. Silver halide photographic emulsion containing predominantly silver bromide
EP0185243A2 (en) 1984-12-17 1986-06-25 Minnesota Mining And Manufacturing Company Photosensitive silver halide material for obtaining half-tone black-and-white images and method for half-tone high-contrast reproduction
US4888273A (en) * 1988-02-26 1989-12-19 Polaroid Corporation Stabilized tabular silver halide grain emulsions

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FR1158160A (fr) 1958-06-11
GB814823A (en) 1959-06-10

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