Classifications

• • 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
  • G03C5/305—Additives other than developers

Definitions

• This invention relates to photographic processing solutions and methods. In one of its aspects, it relates to monobath compositions and processes for development of silver images in photographic silver salt layers of photographic elements. In another of its aspects, it relates to the use of mercapto organic acids, particularly alkyl-substituted mercapto organic acids, for the stabilization of monobaths.
• Developing solutions employed for such purposes which contain silver halide solvents often dissolve undesired concentrations of silver salt from a silver salt layer of a photographic element. This is then reduced by developing agent present to finely divided metallic silver which forms a sludge in the solution.
• developing agent present to finely divided metallic silver which forms a sludge in the solution.
• the solvent action is extended by sodium sulfrte which has a weak capacity to dissolve silver halide.
• sludge may deposit on parts of the equipment employed for processing, such as rollers, belts, etc., as a scale which may clog orifices or scratch film. It may also deposit as a stain on'the surface of films and papers, which lowers photographic quality. Consequently, it is extremely desirable to minimize such deposition.
• a monobath composition comprising an alkaline solution of a hydroxylamine or 3-pyrazolidone developing agent and a monothioglycerol, thioglycol, beta-mercaptoethylamine, N,N-diethyl-beta-mercaptoethylamine or 2- thiobarbituric acid.
• U.S. Pat. No. 3,255,008, issued June 7, 1966, to William J. Tefft discloses monobath solutions containing thioglycolic acid (mercaptoacetic acid), beta-mercaptopropionic acid, mercaptosuccinic acid, and 3-mercapto-l ,2- propanediol.
• U.S. Pat. No. 3,252,787 to Dave R. Kazen, issued May 24, l966 discloses the use of thiomaleic or mercaptosuccinic acid in monobath developing and fixing solutions.
• An object of the invention is accordingly to provide a photographic processing solution and method which is resistant to sludging.
• R is hydrogen or lower alkyl, i.e. an alkyl group having one to five carbon atoms such as' methyl, ethyl, propyl, butyl, and pentyl;
• R, is a lower alkyl as described; and
• R, and R, are each selected from the group consisting of hydrogen; alkyl, e.g. alkyl containing one to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl and eicosyl; amino groups,
• R is hydrogen or lower alkyl, as described; hydroxyl; and halogen, i.e. fluorine, chlorine, bromine and iodine; and m is zero or an integer from 1 to 5; provides unexpectedly good resistance to sludging, e.g. resistance to formation of undesired concentrations of colloidal silver or other undesired deposits which can adversely affect processing of an exposed photographic silver salt layer of a photographic element in such processing solution or photographic process. It has been found that compounds within formula I wherein m is 0, such as mercaptoisobutyric acid, are especially suitable antisludging agents for use in liquid photographic processing solutions and in processes employing these solutions. Compounds of described formula I are surprisingly more effective, or, as effective but at lower concentrations than closely related mercaptoacetic acid and 3-mercaptopropionic acid as described in following examples l5, 16, 20 and 21.
• Examples of suitable compounds within formula I include:
• One of the embodiments of the invention is a monobath comprising an antisludging agent of formula I as described.
• monobaths are well known, as set out for example in The Monobath Manual," by Grant M. Haist, l966. Any monobath and/or monobath process can be employed according to the invention in which it is desirable to have resistance to sludging and in which compounds within formula I as described are effective.
• the antisludging agents within formula I are also effective in a wide range of other photographic processing solutions and in general can be employed in photographic processing solutions and/or processes where resistance to sludging is desired.
• compounds within formula I are especially effective in thiosulfate monobaths, they can also be employed in a developer solution, a development activator solution, a fixing solution, a stabilizing solution, a gelatin hardener solution, a solution designed for rapid access processing, e.g. thiocyanate solutions, such as alkali metal thiocyanate and/or ammonium thiocyanate solutions, and the like. Solutions of these types are well known and described, for instance, in "The Theory of the Photographic Process, Mees et al., Third Edb tion, 1966, MacMillan Company.
• Typical processing solutions according to the invention are aqueous solutions, but other solvents can be employed if desired, or can be employed in combination with water.
• organic solvents such as an organic amine and/or hydroxyl amine solvents, e.g. propyl amine, butyl amine, Z-aminoethanol, Z-methylaminoethanol, Z-ethyIaminoethanol, diethanol amine(2,2-iminodiethanol), Z-aminopropanol, morpholine, and the like.
• organic solvents can have other affects than solvent action, e.g. they can be development activators.
• the exact quantity of the antisludging agent or antisilvering agent within formula I needed is dependent upon a number of factors, such as pH and silver solvency of the processing solution, temperature of processing, nature and silver coverage of the photographic element processed, degree of exhaustion of the processing solution, and other factors.
• certain developer solutions can require considerably less of the described antisludging agent than a monobath.
• developers require less than 0.5 gram of the described antisludging agent per liter of processing solution for normal usage. Usually 0.05 to 0.5 gram per liter is sufficient, but highly alkaline monobaths for high temperature processing may require 5 to grams per liter of solution.
• the ordinarily employed silver halide developing agents for producing a developed silver image can be used in solutions and processes of the invention. Especially useful results have been obtained using the well known 3-pyrazolidone developing agents. Typical of pyrazolidone developing agents useful in the monobath compositions of the invention are set out in British Pat. No.
• 930,572 including l-phenyl-3-pyrazolidone, l-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-5-methyl-3- pyrazolidone, l-phenyl 4-methyl-3-pyrazolidone, l,5-diphenyl-3-pyrazolidone, l-p-tolyl-3-pyrazolidone, l-phenyl-Z- acetyl-4,4-dimethyl-3-pyrazolidone (acetyl group hydrolysis off to yield active developing agent), l-p-hydroxyphenyl-4A- dimethyl-B-pyrazolidone, l-(2-benzothiazolyl)-3- pyrazolidone, 3-acetoxy'l-phenyl-3-pyrazolidone (acetoxy group hydrolysis off to yield active developer), etc.
• 3- pyrazolidone developing agents are particularly useful and they can be incorporated partly or wholly within the photographic element undergoing development. However, for rapid monobath processing, it is desirable to generally have sufficient pyrazolidone developing agent in the aqueous developing solution to effect rapid processing.
• Other black-and-white photographic developing agents which can be employed alone or in combination with the 3-pyra2olidone include, for example, polyhydroxy benzenes, such as hydroquinone developing agents, e.g.
• hydroquinone alkyl-substituted hydroquinone, such as t-butylhydroquinone, methylhydroquinone, dimethylhydroquinone; catechol and pyrogallol; chloro-substituted hydroquincnes, such as chlorohydroquinone, or dichlorohydroquinone; alkoxy-substituted hydroquinone, such as methoxy or ethoxy hydroquinone; aminophenol developing agents, such as N-methyl-p-aminophenol and 2,4- diaminophenols; ascorbic acid developing agents; N-methyl-paminophenol sulfate, pyrazolones such as 4aminopyrazolone; etc.
• chloro-substituted hydroquincnes such as chlorohydroquinone, or dichlorohydroquinone
• alkoxy-substituted hydroquinone such as methoxy or ethoxy hydroquinone
• the concentration of the developing agent in the monobath composition can be varied, depending upon the particular photographic material undergoing development.
• the 3-pyrazolidone developing agents are particularly useful, since they can be incorporated directly into the photographic material either in a layer contiguous to the emulsion layer or in the emulsion layer itself (particularly where a development precursor is used, such as 3-acetoxy-lphenyl-B-pyrazolidone).
• the photographic processing solutions, especially the monobath compositions, of the invention can comprise any of the conventional watensoluble fixing agents, typically thiosulfate fixing agents, such as alkali metal, e.g. sodium, potassium, and lithium thiosulfates, ammonium thiosulfate, etc.
• concentration of the thiosulfate compound can be varied, but it is important to have the concentration sufficiently high to fix or stabilize the desired concentration of the unexposed silver halide.
• the thiosulfate concentration should be at least about grams per liter of monobath.
• the maximum concentration of thiosulfate is primarily a function of the concentration of the silver halide in the emulsion being processed. Frequently, concentrations as high as grams of thiosulfate per liter of monobath composition can be employed and good quality prints can be produced in 5 seconds or less using such compositions. Of course, if the concentration of silver halide in the emulsion is increased, then it is possible that amounts of thiosulfate in excess of 160 grams per liter can be employed. Overfixing is of course to be avoided.
• Suitable antifoggants include organic antifoggants, such as benzotriazole, benzimidazole, Z-mercaptobenzimidazole and mercaptotetrazole antifoggants.
• organic antifoggants such as benzotriazole, benzimidazole, Z-mercaptobenzimidazole and mercaptotetrazole antifoggants.
• inorganic antifoggants ineluding potassium bromide, potassium iodide and/or sodium bromide, can be employed in the photosensitive element and/or monobath composition of the invention. Any suitable amount of antifoggant can be employed, depending on the components of the monobath composition, the photosensitive element, and the like.
• Processing according to the practice of the invention can be carried out under any suitable conditions, usually ambient conditions, e.g. about 20 C. to about 30 C. However, higher temperatures can be employed if desired. Particularly where rapid processing is to be carried out, temperatures about 60 C. can be used.
• the time for processing employing the compositions and processes of the invention can vary from about a second to several minutes or more depending on the desired image, processing conditions and the like.
• Any development activator and any suitable concentration of development activator can be employed in the solutions of the invention which provides the desired alkalinity or pH to effect the desired development.
• Typical development activators include inorganic development activators such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, and potassium carbonate, as well as organic activators, such as organic amines, e.g. hydroxyalkyl amines, such as ethanolamine, morpholine, propanolamine, and the like.
• the pH of solutions of the invention e.g. monobaths, can vary over wide ranges, but in general a pH of at least 9 is employed, e.g. preferably about 10.0 to about 13.
• compositions and processes of the invention are suitable for developing and fixing a wide variety of photosensitive emulsions, especially silver halide-gelatin photosensitive emulsions.
• the photosensitive emulsions which can be developed and fixed with the compositions and processes of the invention include those which are nonspectrally sensitized, such as X-ray type emulsions, or emulsions which are orthochromatic, panchromatic, infrared sensitive, and the like, containing spectral sensitizing dyes.
• Spectral sensitizers which can be used in a photosensitive emulsion processed according to the invention include cyanines, mercocyanines, styryls, and the like.
• photographic elements employed in the practice of the invention can be sensitized by using any of the well-known techniques used in emulsion making, e.g. by digesting with naturally active gelatin or various sulfur, selenium, noble metal and/or gold compounds.
• colloids can be used alone or in combination as one lz'hlch l of exposed film having a highvehicles or binding agents where one is used in the photosensispeed, fihe'gl'aihed silver chlol'ohl'omide emulsion y is tive emulsions and elements employed in the practice of the developed 6 minutes ahohi in 500 of the invention Among such mamfials are the natural and/0
• the solution is clear and colorless before Synthetic binding materials generally employed for this pub the film is processed and the solution is clear and colorless pose including, for example, gelatin, colloidal albumin, waterafter 24 hours after the mm Processed No Sludgmg soluble vinyl polymers, and polysaccharides, polyvinylpyr- Parem' rolidone and the like.
• the vehicle or binding agents can contain dispersed 25 polymerized vinyl compounds, particularly those which in- This is a comparative example demonstrating advantages of crease the dimensional stability of photographic materials. the invention.
• Suitable synthetic polymers of this type include water-insolu- Development of exposed film of example 1 is repeated in a ble polymers of alkyl acrylates and methacrylates, acrylic monobath as in example 1 except no antisilvering compound acid, sulfoalkyl acrylates or methacrylates and the like. is' present.
• the clear and colorless monobath solution The silver salts processed according to the invention include becomes hazy immediately after processing the film. Within 2 any of the photosensitive silver salts, such as any of the hours, silver sludge begins to settle to the bottom. A very photosensitive silver halides.
• Suitable silver halides include, h y tan-colored sludge deposits from the y solution after for example, silver bromide, silver iodide, silver chloride or 24 hoursmixed halides, such as silver chlorobromide, silver bromoiodide, and the like.
• Preferred silver halides are those in EXAMPLE 3 which the halide P at least 50 mole Percent chlol'ide- This is a comparative example serving to further illustrate
• the silver halides used can be those which form latent images h ff ti f mi m i agents according to the predominately on the surface of the silver halide grains or vention.
• the developer solution is clear and colorless without any appearance of sediwhereihRishydl'ogeh01'lowelalkyliRiisiowefalkyl;and 2 mentation.
• the used and s each Selected from the P consisting of y g developer is clear and colorless, still without any evidence of alkyl, amine, hydroxyl and halogen; m is zero or an integer silver precipitation. from I to S.
• This process is especially useful in preventing Repeating example i, but with the compounds used below sludging in monobaths, e.g. thiosulfate monobaths, as the results are as follows:
• H CH C-C 0 on 13
• O K CH (
• HSCHz(IJHCO0H 26 4-S-thiuroniumbutane sulionate do Clear, pale yellow.. Hazy, light yellow it floating particles, heavy sludge, slight plating. H N
• Beta-phenyl-alpha-mercaptoeoryiic acid Yellow, white Hazy, yellow,white. Hazy, brown solution, some floating particles. particles, ray-brown sludge. considerable p ating.
• C H Z- C O OH 36 Isothiureidoacetio acid Clear, white com- Yellowish, white Clear colorless, floating pa i le pound particles. compound. dark brown sludge, no plating.
• a liquid photographic processing solution comprising an antisludging agent which is a mercapto organic acid of the formula:
• a liquid photographic processing solution as in claim 1 comprising a developer solution.
• a liquid photographic processing solution as in claim I wherein said mercapto organic acid is mercaptoisobutyric acid.
• a liquid photographic processing solution as in claim 1 comprising a monobath and wherein said mercapto organic acid is mcrcaptoisobutyric acid.
• a liquid photographic processing solution as in claim 1 comprising a monobath containing a thiosulfate fixing agent and wherein said mercapto organic acid is mcrcaptoisobutyric acid.
• a liquid photographic processing solution as in claim I 5 comprising a monobath containing 0.05 to 0.5 gram per liter of said mercapto organic acid.
• a liquid photographic processing solution as in claim 1 comprising a monobath containing:
• a liquid photographic processing solution as in claim 10 who-rein said gelatin-hardening agent is a glutaraldehy de ($53) Zion "l l wherein R is hydrogen or lower alkyl; R is lower alkyl; and R,1-'
• R are each selected from the group consisting of hydrogen, alkyl, amine, hydroxyl and halogen; m is zero or an integer from I to 5.
• a photographic method as in photographic silver salt layer is a photographic silver halide f emulsion layer. 1
• a photographic method comprising developing and fix- 1 ing an image in an exposed photographic silver salt layer of a photographic element containing a silver halide developing j agent by contacting said photographic element with a photo- 1 graphic processing solution resistant to sludging comprising:
• monobath comprises a thiosulfate fixing agent, a silver halide developing agent and mercaptoisobutyric acid.
• R is hydrogen or lower alkyl; R, is lower alkyl; and R, and R, are each selected from the group consisting of hydrogen, alkyl, amine, hydroxyl and halogen; m is zero or an integer from 1 to 5.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Citations (6)

• 1968
  • 1968-02-27 US US708529A patent/US3628955A/en not_active Expired - Lifetime
• 1969
  • 1969-02-26 FR FR6904933A patent/FR2002685A1/fr not_active Withdrawn
  • 1969-02-27 BE BE729077D patent/BE729077A/xx unknown
  • 1969-02-27 GB GB1251558D patent/GB1251558A/en not_active Expired

Patent Citations (6)

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