US3440049A - Polyhydroxy-spiro-bis-indane photographic tanning agent - Google Patents

Polyhydroxy-spiro-bis-indane photographic tanning agent Download PDF

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Publication number
US3440049A
US3440049A US554970A US3440049DA US3440049A US 3440049 A US3440049 A US 3440049A US 554970 A US554970 A US 554970A US 3440049D A US3440049D A US 3440049DA US 3440049 A US3440049 A US 3440049A
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Prior art keywords
indane
emulsion
bis
spiro
tanning
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US554970A
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Jerome Albert Moede
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EIDP Inc
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EI Du Pont de Nemours and 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
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C5/3021—Developers with oxydisable hydroxyl or amine groups linked to an aromatic ring
    • 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
    • G03C5/29—Development processes or agents therefor
    • G03C5/315—Tanning development

Definitions

  • Tanning developing agents have been incorporated in photographic emulsions and developers for many years.
  • soluble tanning developing agents such as pyrocatechol and hydroquinone are subject to disadvantages such as fogging during aging, loss of speed during aging, and diffusion throughout the gelatin causing tanning of the contiguous nonimage areas.
  • Some water-insoluble tanning agents in addition to the disadvtanges listed, are further limited because of sublimation during aging to yield unstable sensitometric properties and because they harden the unexposed emulsion and impair wash-off. It is, therefore, an object of this invention to provide new tanning agents which minimize or eliminate these unwanted effects.
  • This invention in its broadest sense encompasses developing a photosensitive silver halide in the presence of an alkyl hydroxy-spi'ro-bis-indane having ortho or para-sustituted hydroxyl groups in at least one of the aromatic rings.
  • This group of compounds can be incorporated in the photosensitive silver halide emulsion, in the processing solution, or as an auxiliary layer in a multiple layer photosenstvie element, and has been found to have good developing properties for exposed or latent silver halide images and an excellent tanning action on water permeable colloids, especially gelatin. 7
  • a suspensoid a colloidal system having solid particles dispersed therein, is prepared by neutralizing an alkaline solution containing up to about 5% by weight of the agent 3 ,3 ,3 ,3 -tetramethyl-5 ,6,5,6'-tetr-ahydroxy-spiro-bisindane, thereinafter referred to as indane (I), gelatin in amounts of approximately 1 to 10% and a water-miscible solvent for indane (I), e.g., Z-methoxyethanol in amounts of 0 to 10%, (all percentages being by weight).
  • indane indane
  • gelatin in amounts of approximately 1 to 10%
  • a water-miscible solvent for indane (I) e.g., Z-methoxyethanol in amounts of 0 to 10%, (all percentages being by weight).
  • the resulting mixture is then mixed with an unhardened gelatino-silver halide emulsion such that the effective concentration of indane (I) is in the range of approximately 0.01 mole to 0.3 mole of indane (I) per mole of silver halide.
  • the photosensitive silver halide emulsion containing indane (I) is then coated on a matted support as disclosed in assignees pending applications, Moede Ser. Nos. 339,849, Jan. 24, 1964, now Patent No. 3,353,- 958, and Moede et al. 517,894, Ian. 3, 1966.
  • the photo sensitive element containing the tanning agent, indane (I) After exposure through a negative to actinic radiation, the photo sensitive element containing the tanning agent, indane (I), is processed in an alkaline medium, usually a 5% aqueous potassium carbonate solution. Indane (I) develops the silver image and its oxidized form tans the gelatin in the image area while in the nonimage area, which is removed by washing in warm Water, no tanning occurs. After washing in water, there remains a tough tanned silver-gelatin image in relief on the matted support.
  • an alkaline medium usually a 5% aqueous potassium carbonate solution.
  • Indane (I) develops the silver image and its oxidized form tans the gelatin in the image area while in the nonimage area, which is removed by washing in warm Water, no tanning occurs. After washing in water, there remains a tough tanned silver-gelatin image in relief on the matted support.
  • the resulting emulsion was coated on a subbed, matted polyester support as described in assignees pending patent application, Ser. No. 339,849 filed on J an. 24, 1964.
  • the emulsion coating was at a level of 20 mg. of AgCl/ d1m.
  • the coated emulsion was then allowed to dry.
  • the photosensitive element exhibited the following sensitometric and physical properties:
  • Example III demonstrates that the alkyl hydroxy-spirobis-indane having ortho or para-substituted hydroxyl groups on the aromatic rings may be incorporated in the developer solution rather than the emulsion layer.
  • Example II The emulsion was exposed to a negative as in Example I.
  • a developer solution A was prepared as follows.
  • the exposed photosensitive element was developed in solution A for one minute at 68 F.
  • the exposed area developed and tanned while the unexposed area exhibited no tanning effect or development.
  • the unexposed area was washed 01f in warm water leaving a gelatin-silver image in relief on the matted surface, of the support.
  • indane (I) To further demonstrate the tanning characteritsics of indane (I), the same emulsion as used in Example III was exposed and developed as was done in the first half of this example except that the developer did not contain any of the tanning agent, indane (I). There was no image development in the plain carbonate developer thus indicating the usefulness of indane (I) as a tanning agent and as a developer which reduces exposed silver halide to silver.
  • suspensoid A The components of suspensoid A were mixed, resulting in a hazy mixture. To produce a clear greenish-blue mixture with a pH of 11.5, 1 ml. of 3 M NaOH was added to the mixture. The mixture was slowly neutralized with 6.5 ml. of 1.5 N H 50 producing a pH of 6.5 and a precipitate of indane (I).
  • aqueous gelatin 150 Washed AgCl emulsion (mole of AgCl) 0.15 2% methanol solution of phenylbiguanide mercaptobenzothiazole 20 10% ethanol solution of propyl gallate 20 Aqueous tartrazine (Cl. 640) Sodium lauryl sulfate 7.5
  • Example II The resulting emulsion, having a pH of 5.8 was then coated on a matted support as in Example I.
  • the coated emulsion was then aged, exposed and developed as in Example I.
  • the sensitometric and physical properties were as follows:
  • Component 1- 7.2% aqueous gelatin gm 1725 10% aqueous Na SO gm 17 3 M NaOH ml 25
  • Component 2-- 2-methoxyethanol ml 186 Methanol ml 194
  • Phenylbiguanide Mercapto benzothiazole gm 4
  • Propyl gallate gm 20 3,3,3',3-tetramethyl-5,6,5,6'-
  • a developer was prepared as follows.
  • Example V was repeated except that /a of the gelatin in the photographic emulsion was replaced with a gelatinpolymer component prepared by copolymerizing 8 parts Fog Relative D max Melting speed 1 min. 3 min. point dev. dev. F.)
  • Example I was repeated except that all ingredients Were reduced to to the scale in Example I and addition (5) was a mixture of 4 grams of indane II, 32 ml. of dimethyl formamide, ml. of ethyl alcohol and 48 ml. of water. Indane II was prepared according to the procedure of Fisher, Furlong and Grant in J. Am. Chem. Soc., 58: 820-2 (1936), Example VI.
  • the emulsion coating was at a level of mg. of AgCl/dm. and exhibited the following sensitometric and physical properties:
  • the preferred tanning development agent of this invention is 3,3,3',3-tetramethyl- 5,6,5,6-tetrahydroxy-spiro-bis-indane (indane I).
  • Indane (I) can be prepared by contensation of catechol with acetone such as the process disclosed by Baker, J. Chem. Soc., 1934, pp. 167881. Satisfactory results were obtained using 3,3,3',3 tetramethyl 4,6,7,4,6,7 hexahydroxy-l,1-spiro-bis-indane (indane II).
  • Indane II can be prepared by the condensation of polyhydric phenols with acetone as disclosed by Fisher, Furling, and Grant, I, Am. Chem.
  • the tanning development agent is usually added to the emulsion as a suspensoid.
  • the novel process for making a suspensoid is not limited to that disclosed in the examples as other techniques such as those listed in books on colloidal chemistry can be used to prepare a suspensoid of polyhydroxy-spiro-bis-indanes.
  • indanes can also be added to the emulsion directly as a solute in a water-miscible organic solvent or as a solute in the oil phase of an oil-water dispersion.
  • the novel tanning developing agents of this invention may be used in all conventional hardened or unhardened photographic emulsions.
  • indanes may be used in the developers or in combination with other developers, These indanes may also be used in processing mediums such as pods or packets for inverse transfer systems. These indanes, e.g., I and II, may be added to auxiliary layers of the photographic system and may be used alone or in combination with other nontanning or tanning developing agents, e.g., alkyl gallates and hydroquinone.
  • nontanning or tanning developing agents e.g., alkyl gallates and hydroquinone.
  • the silver halide emulsion may be selected from Well known emulsions containing silver chloride, silver bromide, and silver iodide or mixtures thereof.
  • the use of this class of novel tanning development agents is particularly useful in wash-off type emulsions, or precipitated and coagulated washed emulsions such as those disclosed in assignees US. Patent 2,772,165 by Moede.
  • the preferred binder for use with this novel tanning development agent is gelatin.
  • other natural or synthetic water-permeable organic colloid binding agents susceptible to cross linked quinone tannage can be used.
  • Such agents include water-permeable or water-soluble polyvinyl alcohol and its derivatives, e.g., partially hydrolyzed polyvinyl acetates, polyvinyl ethers, and acetals containing a large number of extra linear -CH CHOH groups; hydrolyzed interpolymers of vinyl acetate and unsaturated addition polymerizable compounds such as maleic anhydride, acrylic and methacrylic acid ethyl esters, and styrene.
  • Suitable colloids of the last mentioned type are disclosed in US.
  • the useful polyvinyl acetals include polyvinyl acetaldehyde acetal, polyvinyl butyraldehyde acetal and polyvinyl sodium o-sulfobenzaldehyde acetal.
  • Other useful colloid binding agents include the poly-N-vinyl lactams of Bolton US. Patent 2,495,918, the hydrophilic copolymers of N-acrylamidoalkyl betaines described in Shacklett US. Patent 2,833,650 and hydrophilic cellulose ethers and esters.
  • the film support for the emulsion layers used in the novel process may be any suitable transparent plastic.
  • the cellulosic supports e.g., cellulose acetate, cellulose triacetate, cellulose mixed esters, etC.
  • Polymerized vinyl compounds e.g., copolymerized vinyl acetate and vinyl chloride, polystyrene, and polymerized acrylates may also be mentioned.
  • the film formed from the polyesterification product of a dicarboxylic acid and a dihydric alcohol made according to the teachings of Alles, US Patent 2,779,684, and the patents referred to in the specification of that patent.
  • Other suitable supports are the polyethylene terephthalate/isophthalates of British Patent 766,290 and Canadian Patent 562,672 and those obtainable by condensing terephthalic acid and dimethyl terephthalate with propylene glycol, diethylene glycol, tetramethylene glycol or cyclohexane 1,4-dimethanol (hexahydro-p-xylene alcohol).
  • the films of Bauer et al. US. Patent 3,052,543 may also be used.
  • the above polyester films are particularly suitable because of their dimensional stability.
  • adjuvants used to make a suspensoid of indane' (I), e.g., water miscible solvents such as rnethoxy-ethanol various adjuvants may be added to the emulsion. These include surfactants such as sodium dodecyl sulfate, auxiliary developers, and other tanning agents such as propyl gallate, alkyl gallates, and hydroquinone.
  • the emulsion can contain dyes, e.g., tartrazine (Cl. 640); toners, e.g., phenyl biguanide mercapto benzothiazole, and similar compounds such as those disclosed in assignees US. Patent 2,668,113; hardeners, e.g., chrome alum, formaldehyde; matting agents; optical brightening agents; image color modifiers; sensitizers; optical sensitizers; etc.
  • dyes e.g., tartrazine (Cl. 640)
  • tanning development agents such as indane (I) are especially beneficial in making reproductions of drawings, maps, line copy, half tones, etc., wherein a reproduction can be easily revised by drawing on the matte surface and/or wet erasing the relief image.
  • an agent such as Indane (I), having ortho or para-substituted hydroxyl groups on the aromatic rings is especially useful with any binder that is subject to quinone tannage.
  • Indane (I) has specific advantages over the use of other tanning development agents. It is nonvolatile. This is important when the agent is added to the photographic product at the time of manufacture for it does not cause product instability through volatilization during aging as does catcchol and tertiary butyl catechol.
  • indane (I) and its oxidation product are nonmigratory. This limits the tanning effect during development to the image area and does not cause wandering to the contiguous nonimage area.
  • Thi property provides excellent wash-off definition.
  • the silver image can be removed by bleaching in a known manner and elements containing indane (I) can be used for well known process of dye imbibition.
  • a process which comprises developing an exposed silver halide emulsion in the presence of a polyhydroxyspiro-bis-indane.
  • a process which comprises developing a latent silver halide image in a water-permeable colloid binding agent in an aqueous alkaline developer solution containing a p0lyhydroxy-spiro-bis-indane.
  • a suspension of light-sensitive silver halide grains in a water-permeable colloid said suspension containing per mole of silver halide about 0.01 mole to about 0.3 mole of a polyhydroxy-spiro-bis-indane.
  • a suspension as defined in claim 3 wherein said colloid is a mixture of gelatin and a vinylidene chloride/ alkyl acrylate copolymer.
  • a suspension as defined in claim 3 wherein said colloid is a mixture of gelatin and a vinylidene chlorine/ methyl acrylate copolymer.
  • a suspension as defined in claim 3 wherein said colloid is gelatin and said indane is 3,3,3',3'-tetramethyl- 4,6,7,4',6,7-hexahydroxy-1,1-spiro-bis-indane.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US554970A 1966-06-03 1966-06-03 Polyhydroxy-spiro-bis-indane photographic tanning agent Expired - Lifetime US3440049A (en)

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3909263A (en) * 1972-12-14 1975-09-30 Fuji Photo Film Co Ltd 5,5{40 ,6,6{40 -Tetrahydroxy-3,3,3{40 ,3{40 -tetramethyl-bis-spirohydrindene auxiliary developers
FR2449904A1 (fr) * 1979-02-26 1980-09-19 Fuji Photo Film Co Ltd Materiau photographique a l'halogenure d'argent contenant des agents developpateurs tannants
US4299909A (en) * 1979-08-07 1981-11-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4335197A (en) * 1980-11-25 1982-06-15 E. I. Du Pont De Nemours And Company Photoimaging process
US4346167A (en) * 1980-07-29 1982-08-24 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material and process for producing silver halide photographic emulsion
WO1985004025A1 (en) * 1984-03-02 1985-09-12 Minnesota Mining And Manufacturing Company Photographic tanning developer formulation
US4576894A (en) * 1984-09-24 1986-03-18 E. I. Du Pont De Nemours And Company Tanning development in low silver photoimaging using polymeric couplers
US4588673A (en) * 1982-06-30 1986-05-13 Fuji Photo Film Co., Ltd. Retouchable mat film
US4705738A (en) * 1985-03-18 1987-11-10 Minnesota Mining And Manufacturing Company Silver halide photographic material for tanning development and process of producing a relief image
US4725533A (en) * 1985-02-25 1988-02-16 Fuji Photo Film Co., Ltd. Silver halide photographic material for wash-off relief image
EP0687572A1 (en) 1994-06-15 1995-12-20 Agfa-Gevaert N.V. Thermosensitive recording method
EP0775592A1 (en) 1995-11-27 1997-05-28 Agfa-Gevaert N.V. Thermal image-forming process
EP0775595A1 (en) 1995-11-27 1997-05-28 Agfa-Gevaert N.V. Thermographic recording material with phosphoric acid and derivative as lubricant
EP0782043A1 (en) 1995-12-27 1997-07-02 Agfa-Gevaert N.V. Thermographic recording material which improved tone reproduction
EP0845709A1 (en) 1996-11-29 1998-06-03 Agfa-Gevaert N.V. A heat sensitive imaging element and a method for producing lithographic plates therewith
WO2015148028A1 (en) 2014-03-24 2015-10-01 Carestream Health, Inc. Thermally developable imaging materials
WO2016073086A1 (en) 2014-11-04 2016-05-12 Carestream Health, Inc. Image forming materials, preparations, and compositions
WO2016195950A1 (en) 2015-06-02 2016-12-08 Carestream Health, Inc. Thermally developable imaging materials and methods

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1092648B (de) * 1958-12-11 1960-11-10 Riedel De Haeen Ag Chemische F Verfahren zum Stabilisieren von Polyolefinen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1092648B (de) * 1958-12-11 1960-11-10 Riedel De Haeen Ag Chemische F Verfahren zum Stabilisieren von Polyolefinen

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3909263A (en) * 1972-12-14 1975-09-30 Fuji Photo Film Co Ltd 5,5{40 ,6,6{40 -Tetrahydroxy-3,3,3{40 ,3{40 -tetramethyl-bis-spirohydrindene auxiliary developers
FR2449904A1 (fr) * 1979-02-26 1980-09-19 Fuji Photo Film Co Ltd Materiau photographique a l'halogenure d'argent contenant des agents developpateurs tannants
US4283479A (en) * 1979-02-26 1981-08-11 Fuji Photo Film Co., Ltd. Silver halide photographic materials and a process forming relief images
US4299909A (en) * 1979-08-07 1981-11-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4346167A (en) * 1980-07-29 1982-08-24 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material and process for producing silver halide photographic emulsion
US4335197A (en) * 1980-11-25 1982-06-15 E. I. Du Pont De Nemours And Company Photoimaging process
US4588673A (en) * 1982-06-30 1986-05-13 Fuji Photo Film Co., Ltd. Retouchable mat film
WO1985004025A1 (en) * 1984-03-02 1985-09-12 Minnesota Mining And Manufacturing Company Photographic tanning developer formulation
US4699868A (en) * 1984-03-02 1987-10-13 Minnesota Mining And Manufacturing Company Photographic tanning developer formulation
US4576894A (en) * 1984-09-24 1986-03-18 E. I. Du Pont De Nemours And Company Tanning development in low silver photoimaging using polymeric couplers
US4725533A (en) * 1985-02-25 1988-02-16 Fuji Photo Film Co., Ltd. Silver halide photographic material for wash-off relief image
US4705738A (en) * 1985-03-18 1987-11-10 Minnesota Mining And Manufacturing Company Silver halide photographic material for tanning development and process of producing a relief image
EP0687572A1 (en) 1994-06-15 1995-12-20 Agfa-Gevaert N.V. Thermosensitive recording method
EP0775592A1 (en) 1995-11-27 1997-05-28 Agfa-Gevaert N.V. Thermal image-forming process
EP0775595A1 (en) 1995-11-27 1997-05-28 Agfa-Gevaert N.V. Thermographic recording material with phosphoric acid and derivative as lubricant
EP0782043A1 (en) 1995-12-27 1997-07-02 Agfa-Gevaert N.V. Thermographic recording material which improved tone reproduction
EP0845709A1 (en) 1996-11-29 1998-06-03 Agfa-Gevaert N.V. A heat sensitive imaging element and a method for producing lithographic plates therewith
WO2015148028A1 (en) 2014-03-24 2015-10-01 Carestream Health, Inc. Thermally developable imaging materials
US9335623B2 (en) 2014-03-24 2016-05-10 Carestream Health, Inc. Thermally developable imaging materials
WO2016073086A1 (en) 2014-11-04 2016-05-12 Carestream Health, Inc. Image forming materials, preparations, and compositions
US9523915B2 (en) 2014-11-04 2016-12-20 Carestream Health, Inc. Image forming materials, preparations, and compositions
WO2016195950A1 (en) 2015-06-02 2016-12-08 Carestream Health, Inc. Thermally developable imaging materials and methods
US9746770B2 (en) 2015-06-02 2017-08-29 Carestream Health, Inc. Thermally developable imaging materials and methods

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DE1572152A1 (de) 1970-04-23
GB1144289A (en) 1969-03-05
BE699429A (enrdf_load_html_response) 1967-12-04

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