US3718469A - Making of a photographic image - Google Patents

Making of a photographic image Download PDF

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Publication number
US3718469A
US3718469A US00082032A US3718469DA US3718469A US 3718469 A US3718469 A US 3718469A US 00082032 A US00082032 A US 00082032A US 3718469D A US3718469D A US 3718469DA US 3718469 A US3718469 A US 3718469A
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United States
Prior art keywords
compound
aldehyde
group
present
developer
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Expired - Lifetime
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US00082032A
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English (en)
Inventor
T Hatano
H Hara
M Sugiyama
R Ohi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/167—X-ray

Definitions

  • R and R are each hydrogen, chlorine, [51] Int. Cl ..G03c 5/26,G03c 5/30, G03c 1/34 b mi hydroxyl group, carboxyl group, carboxyl [58] Field of Search ..96/66.5, 109, 61, 50, 66 group substituted with sodium, potassium ium, sulfoxyl group, or sulfoxyl group substituted with References Cited sodium, potassium or ammonium, wherein at least one UNITED STATES PATENTS of said R and R being a carboxyl group, substituted carboxylate, sulfoxyl group or substituted sulfoxylate, 2,403,927 7/1946 Kendall et al.
  • the present invention relates to a method for making a photographic image and more particularly, it is con- 5 and 2 is a r y lfoxyl, carboxylate 0r sulfoxycerned with a method for making a photographic image using a compound capable of preventing fog caused by aldehyde compounds employed in the hardening of the gelatin layer.
  • a high temperature development process has been known as an effective method of accelerating the development rate of silver halide photographic light sensitive materials.
  • the primary object of the present invention to provide an improved method for high temperature rapid processing which shows neither deterioration of the physical properties of an emulsion layer, nor any substantial increase in fog nor any reduction of developing speed by employing an aldehyde hardening agent together with effective anti-foggants for the aldehyde.
  • R and R are each hydrogen, an alkyl radical or form a hydrocarbon condensed ring therewith.
  • An additional advantage of the present invention is that it is not necessary to add to the light-sensitive material a compound capable of suppressing fog due to an aldehyde hardening agent because the compounds of the present invention are capable themselves of suppressing aldehyde fog effectively in a processing solution, and consequently the deterioration of the lightsensitive material during storage is prevented.
  • the compounds of the present invention are used in a developer together with an aldehyde hardening agent but in another method they may be used in a prehardening solution containing a hardening agent of the aldehyde type.
  • the preferred concentration of the compounds of the present invention in a developer or prehardener containing an aldehyde hardening agent varies within a range of from 20-800 mg, and most preferably, l300 mg per liter of solution, although the quantity of aldehyde present is also a factor.
  • the aldehyde hardening agent of the present invention is a compound having at least one aldehyde group or aldehyde releasing group such as formaldehyde, dimethylolurea, glyoxal or glutaraldehyde, or its sulfite or bisulfite adduct.
  • the developer used in the invention is preferably an aqueous alkali solution containing N- methyl-p-aminophenol sulfate, dihydroxybenzene, 1- phenyl-3 pyrazolidone, phenylenediamine or their derivatives as a developing agent.
  • the developer may further contain various preservatives such as sulfite, alkaline agents such as borax, sodium carbonate, sodium phosphate or caustic soda, hardening agents.
  • the prehardener used in the present invention prior to development may contain, in addition to hardening agents and compounds of the invention, various inorganic salts such as sodium sulfate or magnesium sulfate as well as pH-controlling substances such as borax, sodium phosphate, acetic acid or boric acid.
  • various inorganic salts such as sodium sulfate or magnesium sulfate as well as pH-controlling substances such as borax, sodium phosphate, acetic acid or boric acid.
  • the important feature of the compounds of the present invention resides in their use in a processing solution, but as an alternate method, they may have been incorporated previously in an emulsion (as opposed to a processing solution) so as to prevent fog resulting from the use of aldehyde.
  • a photographic material obtained by adding a compound of the present invention to an emulsion in a proportion of 40-400 mg per 1 g-mole of silver halide before coating is treated with a hardening developer or prehardener containing an aldehyde hardening agent, fog can be maintained at a low level.
  • the prehardener or hardening developer in this case is the same as illustrated above, but free from a compound of the present invention.
  • the present invention is applicable to the processing of light-sensitive materials having a gelation-silver halide emulsion and in particular, for the high temperature rapid treatment of black-and-white and color lightsensitive materials.
  • EXAMPLE 1 An X-ray film subjected to sensitometric exposure using a standard sensitometer was subjected to a high temperature rapid processing of the following procedures.
  • Development Temperature Time 1. Development 39C 40 sec 2. Fixing 35C 5 min 3. Washing 20C 10 min Developer A l-phenyl-B-pyrazolidone 1.5 g hydroquinone 20 g anhydrous sodium sulfite 50 g caustic soda 20 g EDTA (2Na) 3 g S-methyl-benzotriazole 0.200 g potassium bromide 0.8 g water to make 1 liter Developer B Twelve ml (by volume of 25 percent glutaraldehyde was added to 1 liter of Developer A.
  • Developer C Twelve ml (by volume) of 25 percent glutaraldehyde and 0.144 g of Compound 2 were added to 1 liter of Developer A.
  • Developer D Twelve ml (by volume) of 25 percent glutaraldehyde and 0.144 g of Compound 3 were added to 1 liter of Developer A.
  • Developer E Twelve ml (by volume) of 25 percent glutaraldehyde and 0.177 g of Compound 4 were added to 1 liter of Developer A.
  • the fixing solution used was a conventional fixing solution containing sodium thiosulfate as a solvent for the silver halide.
  • EXAMPLE 2 The same X-ray film as that of Example 1 was exposed and developed as follows using three developers.
  • EXAMPLE 3 A commercial high speed negative film was subjected to sensitometric exposure by means of sensitometer and then developed at 20C for 7 minutes using the following four developers.
  • the prehardening and water washing steps prior to the first development may be omitted.
  • the time for the first development is shortened because of elevated temperature.
  • One example for the improved process is as follows:
  • Process Temperature Time 1 First development 40C seconds (hardening development) 2. Water washing 40C 30 seconds The other steps from the red reversal exposure to drying are similar to those of Process 1.
  • Cyan color developer anhydrous sodium sulfite 4-amino-3-methyl-N,N diethylaniline hydrochloride sodium carbonate (monohydrate potassium bromide potassium iodide (0.1% aqueous solution l,5-dihydroxy-2,6-dibromonaphthalene caustic soda water to make by volume EON roman Yellow color forming developer anhydrous sodium sulfite 4 amino-N,N-diethylaniline hydrochloride potassium bromide potassium iodide (0.1% aqueous solution 3-benzolyl-4-(ptoluenesulfonamide) acetanilide caustic soda water to make min 1.
  • the alkaline extract was neutralized with acetic acid, yielding crystals, which were then extracted with 2 l. of toluene, followed by a concentration of the extract. The resulting residue was treated with a small amount of acetone to separate the crystals. The crystals were filtered and washed with a small amount of acetone, dried and recrystallized from acetic acid to give 4 g of yellow needle-like material, mp. 239C (decomp.).
  • EXAMPLE 7 Synthesis of 5-benzol[a]phenazinesulfonic acid (Compound 5 To a hot solution of 5 g of 2-nitroso-l-naphthol-4- sulfonic acid in 50 ml (by volume) of water were added a hot solution of 2 g of O-phenylenediarnine in 30 ml (by volume) of water and 10 ml (by volume) of 6N hydrochloric acid. The resulting solution was heated on a water bath for 10 minutes with stirring. The precipitate was filtered and recrystallized from percent acetic acid to give 5 g of yellow needle-like material, mp. 218C (decomp.).
  • a method for forming a photographic image wherein an exposed gelatinous silver halide photographic material is optionally prehardened, developed, fixed or washed which comprises contacting said exposed gelatinous silver halide photographic material with an aldehyde hardening agent and a compound represented by the following general formula:
  • R and R are each hydrogen, chlorine, bromine, hydroxyl group, carboxyl group, carboxyl group substituted with sodium, potassium or ammonium, sulfoxyl group, or sulfoxyl group substituted with sodium, potassium or ammonium, wherein at least one of said R and R being a carboxyl group, substituted carboxylate, sulfoxyl group or substituted sulfoxylate, and R and R each being hydrogen, an alkyl group, or hydrocarbon ring.
  • a method for forming a photographic image which comprises developing an exposed gelatinous silver halide photographic material with a developer containing a developing agent, an aldehyde or aldehyde releasing agent and a compound of the formula:
  • concentration of the compound of the present invention ranges from 20 to 800 g/liter of solution.
  • concentration of the compound of the present invention ranges from 40 to 400 g/g-mole of silver halide.
  • pH-controlling substances are selected from the group agent is a member selected from the group consisting of 5 consisting of borax, sodium p p acetic a id and N-methyl-p-aminophenol sulfate, dihydroxybenzene, l-phenyl-3-pyrazolidone, phenylenediamine and their derivatives.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00082032A 1969-10-17 1970-10-19 Making of a photographic image Expired - Lifetime US3718469A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8303269 1969-10-17

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US3718469A true US3718469A (en) 1973-02-27

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US (1) US3718469A (de)
DE (1) DE2050919A1 (de)
GB (1) GB1266639A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839046A (en) * 1972-10-12 1974-10-01 Ilford Ltd Process for the production of a photographic print

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2282005A (en) * 1940-03-02 1942-05-05 Eastman Kodak Co Phenazine and naphthazine fog inhibitor for photographic emulsions
US2403927A (en) * 1942-12-03 1946-07-16 Ilford Ltd Improvers for photographic emulsions
US3396023A (en) * 1965-08-24 1968-08-06 Eastman Kodak Co Piazine antifoggants for silver halide emulsions
US3403025A (en) * 1965-08-25 1968-09-24 Eastman Kodak Co Desensitization of silver halides to visible radiation with thiuram disulfides
US3574621A (en) * 1967-04-20 1971-04-13 Ciba Ltd Process for the development of photographic silver images in acid medium 1,4-diazine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2282005A (en) * 1940-03-02 1942-05-05 Eastman Kodak Co Phenazine and naphthazine fog inhibitor for photographic emulsions
US2403927A (en) * 1942-12-03 1946-07-16 Ilford Ltd Improvers for photographic emulsions
US3396023A (en) * 1965-08-24 1968-08-06 Eastman Kodak Co Piazine antifoggants for silver halide emulsions
US3403025A (en) * 1965-08-25 1968-09-24 Eastman Kodak Co Desensitization of silver halides to visible radiation with thiuram disulfides
US3574621A (en) * 1967-04-20 1971-04-13 Ciba Ltd Process for the development of photographic silver images in acid medium 1,4-diazine

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839046A (en) * 1972-10-12 1974-10-01 Ilford Ltd Process for the production of a photographic print

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GB1266639A (de) 1972-03-15
DE2050919A1 (de) 1971-05-06

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