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

• ABSTRACT A developing composition for in photographic materials for printing, containing'an infectious developing agent, sulfite and a hydrazine compound of the general formula: Y
• the developing composition of the invention has good storage stability. 1
• the line and dot images be composed of only a maximum density portion and a background having a minimum density.
• a high-contrast photographic element has the property of forming an intermediate density portion besides a maximum density portion and background, a portion of intermediate density which is termed fringe is always formed around the dot images. The formation of fringe is not desirable for graphic arts because it is deteriorates the dot qualities.
• the fringe can be removed by using a so-called infectious developer which essentially contains a dihydroxybenzene type developing agent and a small amount of sulfite ion.
• a dihydroxybenzene type developing agent for example, hydroquinone is converted into quinone during the developmentprocess and the resulting quinone reacts with sodium sulfite to produce sodium hydroquinone-monosulfonate.
• sodium hydroquinonemonosulfonate is less reductive than hydroquinone due to its low electrode potential, and therefore is almost incapable of acting as a developing agent. Accordingly, the progress of development is not conducted rapidly, thus a fringe is formed.
• the concentration of free sulfite ions is maintained at a low concentration, since sodiu'm sulfite is added in a small amount and since it reacts with a compound having carbonyl groups, such as paraformaldehyde, incorporated in theinfectious develop-- ing agent, in accordance with the following equation:
• Another object of the invention is to provide an infectious developer which is easily controlled before and during development.
• Still another object of the invention is to provide an infectious developer in which the amount of replenishment during development is reduced.
• a further object of the invention to provide a photographic development process for the graphic arts capable of forming line and dot images having good qualities by using an infectious developer stable for a long period of time.
• a hydrazine compound improves remarkably the stability of a developer for the graphic arts.
• the reason a hydrazine compound of the invention improves the stability when added to a developer for graphic arts is not presently understood.
• the hydrazine compounds of the invention give rise to an excellent stability and dot qualities in comparison with conventionally known preservatives such as ascorbie acid or excess amounts of sodium sulfite. Particularly, a slowing of the development speed or a formation of a fringe is not observed in the invention.
• An infectious developer in use, is basically composed of a dihydroxybenzene (developing agent), an alkali, a small amount of sulfite and, if necessary, a sulfite ion buffer.
• the infectious developer of the invention further contains the aforesaid hydrazine compound.
• Dihydroxybenzenes are known in the art and can be easily selected by one skilled in the art. Typical examples of these compounds are hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquionone, toluhydroquinone, 'methylhydroquinone, 2, 3-clichlorohydroquinone, 2,5-dimethylhydroquinone, etc.
• hydroquinone can be practically used. These developing agentsare used singly or in combination. A suitable amount of the developing generally employed.
• a sulfite ion buffer can be used in such an amount that concentration of sulfite is maintained at a low level in the developer.
• buffers are an aldehyde-alkali metal hydrogen sulfite addition product such as formalin-sodium hydrogen sulfite, a ketonealkali metal'hydrogen sulfite addition product such as acetone-sodium hydrogen sulfite addition product, and a carbonylbisulfite-amine condensation product such as sodium bis (2-hydroxyethyl) aminomethane sulfonate.
• the sulfite ion buffer is not limited to the above examples and each ingredient of the addition product or condensation product may be added to the developer.
• the amount of the sulfite ion buffer which is added can range from about- 13 to l30g., preferably 30 to 60g. per one liter of the developer.
• the developing solution can contain further a pH buffer agent, such as an alkanolamine, a water-soluble acid (e. g., acetic acid, boric acid), an alkali (e.g., sodium hydroxide) or a salt (e.g., sodium carbonate). Further, it may contain an alkali metal halide as a development controlling agent.
• a pH buffer agent such as an alkanolamine, a water-soluble acid (e. g., acetic acid, boric acid), an alkali (e.g., sodium hydroxide) or a salt (e.g., sodium carbonate).
• an alkali metal halide as a development controlling agent.
• an organic antifogging agent e.g., benzotriazole, l-phenyl-S-mercapto-tetrazole
• a polyalkylene oxide e.g., 1,3-bis(trimethoxy)-2-butane
• an organic solvent e.g., triethylene glycol, dimethylformamide, methanol, cellosolve
• a characteristic of the infectious developing solution is that the concentration of free sulfite is low.
• a sulfite ion buffer material such as formaldehyde-sodium bisulfite adduct is
• the concentration of free sulfite ions is controlled by the addition of an alkali metal sulfite such as sodium sulfite in an amount of not more than 5 g per lliter of the developing solution as well as a sulfite ion bufier agent.
• Sulfite is generally added in an amount of not more than 3 g per liter of the-developing solution, and thereby the stability of the developing solution is slightly improved, although the dot quality is more or less reduced.
• ifieaiih iiimis' of the present invention improve the inherently poor stability of an infectious developing solution which does not contain an alkali sulfite other than a sulfite ion buffer agent such as a formaldehydesodium bisulfite adduct to a certain extent, they remarkably improve the stability of an infectious developing solution which contains both an alkali sulfite in an amount of not more than 5 g per 1 liter of the developing solution (0.005-0.05 mole of free sulfite) and a sulfite ion buffer agent.'That is to say, the compounds of the present invention excert an effect even ina developing solution which does not contain a free sulfite (e.g., a developing solution which does not contain a sulfite other than formaldehyde-bisulfite adduct), but this effect is very small.
• a free sulfite e.g., a developing solution which does not contain
• the present invention can be employed best in a developing solution containing a small amount of free sulfite.
• a single compound of this invention or a combination of two or more compounds of this invention can 5565156;'riieaifiaifiidrifie compounds of the present invention added to a developing solution varies according to the composition of the developing solution and the kind of the compounds used, but the amount employed generally is in the range of from 0.1
• the developing compounds When the developing compounds are processed prior to use so that they may be readily used as developing solutions on mixing with water or dissolving in water, that is, when they are in the form of liquid or powdered developing compositions, it is effective to incorporate the compounds of the present invention into the developing preprationsbeforehand.
• liquid preparations When liquid preparations are used, it is particularly effective to add the compounds of the present invention since they improve remarkably the stability of the liquid preparations.
• Liquid preparations generally are not known to have a good stability, and therefore it is difficult to obtain a stable developing agent, since the liquid preparations can not contain a large amount of salts (e.g., carbonylbisulfite) due to the characteristics of liquid preparations. Therefore, it is particularly desirable to use the hydrazine compounds of the present invention in liquid preparations.
• a general liquid preparation comprises two liquid compositions, that is, a liquid component containing the developing agent and a liquid component containing an alkali.
• the compounds of the present invention may be incorporated into any such components, but it is particularly effective to add them to the component containing the developing agent. With this treatment, a liquid developing agent having an excellent stability and an infectious developing solution prepared by dilution of said liquid developing agent having a markedly excellent stability, can be obtained.
• solvents for the liquid developing agent there may be used solvents such as water, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, glacial acetic acid or a combination of these solvents.
• solvents such as water, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, glacial acetic acid or a combination of these solvents.
• Light-sensitive materials for printing include common silver halide emulsions (e.g. silver chloride auisiasgsaver chlorbbro mide emulsions, silver chloroiodobromide emulsions).
• common silver halide emulsions e.g. silver chloride auisiasgsaver chlorbbro mide emulsions, silver chloroiodobromide emulsions.
• silver chlorobromide emulsions and silver chloroiodobromide emulsions are suitable for the present invention;
• silver halide-dispersing agents containing these light-sensitive materials hydrophilic colloidal substances, such as gelatin or gelatin derivatives (e.g., collodion), hydroxyethylcellulose, carboxymethylcellulose; water-soluble starches (e.g., dextrin, alkali starch); or hydrophilic polymers (e.g., polyvinylalcohols, polyvinylpyrrolidines, polyacrylamides, polystyrenesulfonic acids) can be used.
• These lightsensitive materials may contain additionally hydrophobic polymers such as polyacrylates, and gelatinplasticizers such as glycerin or trimethanolpropane.
• the emulsions used in these light-sensitive materials may be sensitized using various techniques either when the materials are manufactured or when the materials life applied. For example, they may be chemically sensitized by methods well known in the art, for example, with sodium thiosulfate, alkylthiourea, gold compounds such as complexes of monovalent gold and thiocyanic acid, or mixtures of these. Further, the emulsions may contain heavy metals such as platinum, palladium, iridium, rhodium or cadmium. In addition, the emulsions may be panchromatically or orthochromatically sensitized with color-sensitizers such as cyanine dyes or merocyanine dyes.
• the emulsions may contain dot quality-improving agents such as polyalkyleneoxides and amine compounds (U.S. Pat. No. 3,288,612, German Specification OLS 1,932,882, US. Pat. No. 3,345,175), and sodium benzenethiosulfate, benzenetriazole and l,3,3a,7-tetrazaindene derivatives (U.S. Pat. No. 3,375,114 or U.S. Pat. No. 3,333,959).
• dot quality-improving agents such as polyalkyleneoxides and amine compounds (U.S. Pat. No. 3,288,612, German Specification OLS 1,932,882, US. Pat. No. 3,345,175), and sodium benzenethiosulfate, benzenetriazole and l,3,3a,7-tetrazaindene derivatives (U.S. Pat. No. 3,375,114 or U.S. Pat. No. 3,333,
• the emulsions may be hardened with formaldehyde, resorcylaldehyde dimethylol urea, 2, 4-dichloro-6- hydroxy-l, 3,5-triazine (U.S. Pat. No. 3,325,287) or mucochloric acid, or they may contain surface-active agents such as saponin in order to facilitate the application of the emulsions.
• the emulsions may further contain agents which improve the progress of development such as 3-pyrazolidone derivatives or pyrazolone derivatives. Further, the emulsion may contain development-accelerating agents such as quaternary ammonium salts or cationic surface-active agents.
• the supports used in the present invention are not limited, and glass, cellulose acetate, polystyrene, polycarbonate, polyethylene terephthalate and the like may be used.
• Developing Solution C was prepared by adding 3 g of sodium sulfite additionally to Developing Solution A.
• Developing Solution D was prepared by adding 1 g of ascorbic acid additionally to Developing Solution A.
• Developing Solution A with no additive shows a great decrease in sensitivity when aerated.
• Developing Solution C containing 3.0 g of added sodium sulfite shows a smaller decrease in sensitivity than the Developing Solution A does, but is greatly deteriorated and the dot quality of the fresh solution is poor.
• the hiterto known Developing Solution D containing. 1.0 g of L-ascorbic acid shows almost the same decrease in sensitivity as Developing Solution C when aerated, but this is still unsatisfactory.
• Developing Solution B containing l.0 g of the Compound-2 of the presentinvention shows the smallest decreases in sensitivity "when aerated, and no decrease in the dot quality was observed at all.
• EXAMPLE 2 A lithographic film was prepared was follows. A silver halide emulsion containing 75 mole of silver chloride and 0.2 mole of silver iodide, the remainder of the halide being silver bromide, was subjected to gold sensitization and sulfur sensitization, and then was photosensitized 'with 3-carboxymethyl-5-(2-(3- ethylthiazolinilidene) ethylidene) rhodamine.
• Developing Solution E was prepared by adding Solution l and Solution 2, in this order, to 750 ml of distilled water.
• Developing Solution F was prepared by adding 1.0 g of Compound-3 of the present invention to Solution 1 employed in Developing Solution E, mixing the resulting solution with Solution 2, and making the volume 1 liter.
• Example 2 Each of two liter portions of the developing solution used in Example 2 was placed in two developing apparatus for engraving. In each 200 sheets of a half out lithographic film were processed, with the addition conducted at 20 C using developing solutions of the following compositions:
• R R R and R which can be the same or different, each represents a hydrogen atom, an alkyl group having from one to four carbon atoms, a phenyl group or nitrophenyl group, and wherein one of R R R or R may be a CONHR group in which R represents a hydrogen atom or an amino group,
• said hydrazine is present in an amount ranging from 0.1g to 20.0g per liter of developing solution.
• dihydroxy benzene-type developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, or 2,5-dimethylhydroquinone.
• R and R is a hydrogen atom or methyl group
• R R R and R which can be the same or different, each represents a hydrogen atom, an alkyl group having from one to four carbon atoms, a phenyl group or nitrophenyl group, and wherein one of R,, R R or R may be a CONHR group in which R represents a hydrogen atom or an amino group,
• said hydrazine being present in an amount of from 0.1g to 20.0g per liter of developing solution.
• composition contains formaldehyde-sodium bisulfite adduct.
• dihydroxy' benzene-type developing agent is hydroquinone, chlorohydroquinone, bror'nohydroquinone, isopropylhydroquionone, toluhydroquinone, methylhydroquinone,
• R is a methyl group, an ethyl group or a CONT-l group, wherein R and R is a hydrogen atom or methyl group, and wherein R is a hydrogen atom.

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• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (12)

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• 1971
  • 1971-03-26 JP JP46018123A patent/JPS5115745B1/ja active Pending
• 1972
  • 1972-03-22 US US00237001A patent/US3793027A/en not_active Expired - Lifetime
  • 1972-03-24 FR FR7210487A patent/FR2130687B1/fr not_active Expired
  • 1972-03-24 IT IT49202/72A patent/IT952366B/it active
  • 1972-03-25 DE DE19722214921 patent/DE2214921A1/de active Pending
  • 1972-03-27 GB GB1432472A patent/GB1331403A/en not_active Expired

Patent Citations (9)

Non-Patent Citations (1)

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