US3772022A - Developing composition for use with photographic materials for the graphic arts - Google Patents

Developing composition for use with photographic materials for the graphic arts Download PDF

Info

Publication number
US3772022A
US3772022A US00239978A US3772022DA US3772022A US 3772022 A US3772022 A US 3772022A US 00239978 A US00239978 A US 00239978A US 3772022D A US3772022D A US 3772022DA US 3772022 A US3772022 A US 3772022A
Authority
US
United States
Prior art keywords
developing
composition
developing agent
developing solution
dihydroxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00239978A
Other languages
English (en)
Inventor
E Okutsu
Y Iijima
H Iwano
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3772022A publication Critical patent/US3772022A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 agent for use in photographic materials for the graphic arts, containing an infectious developing agent and acetonitrile, malonitrile or derivatives thereof is disclosed. These nitrile compounds have improved storage stability and prevent air-oxidation.
  • This invention relates to a photographic developer for developing a photographic material for the graphic arts. Particularly, it relates to a developer composition prepared by incorporating acetonitrile, malonitrile or their derivatives into an infectious developing agent, for use with a high contrast photographic negative for the graphic arts. Air-oxidation of an infectious developing agent is prevented and an improvement in stability of the developer is obtained.
  • Photographic line and halftone reproductions are carried out by imagewise exposing a high-contrast or litho-type silver halide photographic element through a cross-screen or contract screen and then developing it with a developer, whereby continuous tone images are converted into photographic line and halftone (dot) images.
  • 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 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 development and the resulting quinone reacts with sodium bisulfite to yield sodium hydroquinone monosulfonate.
  • sodium hydroquinone monosulfonate is less reductive than hydroquinone due to its low electrode potential and is essentially incapable of acting as a developing agent. Accordingly, development does not proceed rapidly, resulting in the formation of a fringe.
  • the concentration of free sulfite ions is kept low, since sodium sulfite is added in a small amount andit reacts with a compound having carbonyl groups, such as paraformaldehyde, incorporated in the infectious developing agent, in accordance with the following equation:
  • Ascorbic acid is, however, poor in stability and hence tends to be decomposed. Particularly, ascorbic acid is readily decomposed when metal ions such as iron ions or copper ions are present, and this leads to the poor stability of the developing solution. Further, ascorbic acid has the disadvantages that the progress of the development is slowed to a certain extent and that the dot quality is reduced when it is added in an large amount.
  • An object of this invention is to provide a photographic developer for a high-contrast photographic element useful for the graphic arts having an excellent preservative property unaccompanied by adverse influences on dot qualities.
  • 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 is 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.
  • R1 RZ C (CHI)BCN .ai in which R R R and n are defined hereinafter increases remarkably the storage stability of a developing solution without exerting any adverse influence on the dot quality.
  • R R and R which can be same or different, represents a hydrogen atom, alkyl group with not more than four carbon atoms, a halogen-substituted alkyl group with not more than four carbon atoms, an alkoxy group with not more than four carbon atoms, COOM in which M represents a hydrogen atom or a water-soluble cation, COR in which R represents an alkyl group with not more than four carbon atoms, CONR'R" in which R and R" represent a hydrogen atom or an alkyl group with not more than four carbon atoms or CN, and n represents or an integer of from 1 to 3.
  • the developing agent for use in a photographic material for the graphic arts can be a general infectious developing agent.
  • 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 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, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, 2, S-dimethylhydroquinone, etc.
  • hydroquinone can be practically used. These developing agents are used singly or in combination.
  • a suitable amount of the developing agent to be added ranges from about 5 to 50g,
  • a sulfite ion buffer can be used in such an amount that the 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(Z-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 g., preferably 30 to 60g. per one liter of the developer.
  • An alkali is added to adjust the developer to an alkaline condition, preferably to a pH higher than 8, more preferably to a pH of 9 to l 1. Accordingly, the addition amount and kind of additive can be freely selected and is not limited to the above examples.
  • the infectious developing agent in addition may contain, a pH buffering agent such as alkanolamines, water soluble acids (e.g., acetic acid or boric acid), a water-soluble alkalis (e.g., sodium carbonate, potassium carbonate, sodium bicarbonate, potassium hydroxide) and salts.
  • a pH buffering agent such as alkanolamines, water soluble acids (e.g., acetic acid or boric acid), a water-soluble alkalis (e.g., sodium carbonate, potassium carbonate, sodium bicarbonate, potassium hydroxide) and salts.
  • the infectious developing agent may contain organic antifogging agents (e.g., benzotriazole, l'phenyl-S- mercaptotetrazole or nitroindazole), lithographic development inhibiting agents and oragnic solvents (e.g., triethyleneglycol, dimethylformamide, methylalcohol, or cellosolve) in an amount of not more than 300 ml per 1 liter of the developing solution.
  • organic antifogging agents e.g., benzotriazole, l'phenyl-S- mercaptotetrazole or nitroindazole
  • lithographic development inhibiting agents e.g., triethyleneglycol, dimethylformamide, methylalcohol, or cellosolve
  • a characteristic of the infectious developing solution is that the concentration of free sulfite ions is low.
  • a sulfite ion buffer solution such as formaldehyde-sodium bisulfite adduct is generally employed.
  • the concentration of free sulfite ions is controlled by addition of an alkali metal sulfite such as sodium sulfite in an amount of not more than 5 g per 1 liter of developing solution as well as sulfite ion buffer solution. Addition of sulfite in an amount of not more than 3 g per l liter of developing solution is generally employed, and this improves slightly the stability of the developing solution, although the dot quality is reduced more or less.
  • the compounds of the present invention improve markedly the poor stability of the infectious developing solution which does not contain alkali metal sulfites other than a sulfite ion buffer solution such as formaldehyde-sodium sulfite adduct, and further improve outstandingly the stability infectious developing solution which contains an alkali metal sulfite in an amount of not more than 5 g per 1 liter of developing solution in addition to a sulfite ion buffer agent.
  • a sulfite ion buffer solution such as formaldehyde-sodium sulfite adduct
  • One compound of the present invention or mixtures of two or more compounds of the present invention can be employed, if desired.
  • the amount of the 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 of the present invention used, but generally the amount added is in the range of from 0.1 to 40 g per l liter of developing solution, more preferably from 0.15 g to g per 1 liter of developing solution.
  • a representative liquid preparation generally comprises two liquid compositions, that is, a composition which contains the developing agent and a composition which contains the alkali agent.
  • the compounds of the present invention may be incorporated into any of these compositions, but is particularly effective to add them to the composition which contains the developing agent.
  • a liquid developing agent having excellent stability, and an infectious developing solution prepared on dilution, having a quite excellent stability, can be obtained.
  • the compounds of the present invention may be added to improve the stability of the developing solution.
  • the developing agents of the present invention are also suitable for high temperature development (i.e., a developing temperature 27C or higher) using an automatic developing apparatus.
  • Light-sensitive materials for the graphic arts which can be used in the present invention, include conventional silver halide emulsions (e.g., silver chloride emulsions, silver chlorobromide emulsions, and silver chloroiodobromide emulsions). Particularly, silver chlorobromide emulsions or silver chloroiodobromide emulsions, containing not less than about 50 mole of silver chloride, more preferably from about 70 to about 95 mole of silver chloride, are suitable for the present invention.
  • silver chlorobromide emulsions or silver chloroiodobromide emulsions containing not less than about 50 mole of silver chloride, more preferably from about 70 to about 95 mole of silver chloride, are suitable for the present invention.
  • hydrophilic colloidal substances such as gelatin or gelatin derivatives (e.g., gelatin, phthalyl gelatin, malonyl gelatin); cellulose derivatives such as hydroxyethylcellulose or carboxymethylcellulose; water-soluble starchs such as dextrin or alkali starch; hydrophilic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide or polystylenesulfonic acid.
  • These light-sensitive materials further may contain hydrophobic polymers such as polyacrylates, and gelatin plasticizers such as glycerin and trimethanol-propane.
  • emulsions employed in these light-sensitive materials can be sensitized on manufacture or by application in accordance with various methods.
  • they may be chemically sensitized according to methods well known in the art, for example, with sodium thiosulfate, alkylthiourea, gold compounds such as complex of monovalent gold and thiocyanic acid, or
  • the emulslons further may contain heavy metals such as platinum, palladium, iridium, rhodium or cadmium.
  • 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 (as disclosed in U.S. Pat. No. 3,288,612, German Specification OLS 1,932,882, U.S. Pat. No.
  • the emulsions may be hardened with hardeners such as formaldehyde, resorcylaldehyde dimethylol urea, 2, 4-dichloro-6-hydroxy-l, 3, 5- triazine (see U.S. Pat. No. 3,325,287) or mucochloric acid, and they may contain surface active agents such as saponin in order to facilitate application.
  • hardeners such as formaldehyde, resorcylaldehyde dimethylol urea, 2, 4-dichloro-6-hydroxy-l, 3, 5- triazine (see U.S. Pat. No. 3,325,287) or mucochloric acid, and they may contain surface active agents such as saponin in order to facilitate application.
  • the emulsions may contain development progress improving agents such as 3-pyrazolidone derivatives or pyrazolone derivatives. Further, the emulsions may contain development accelerating agents such as quaternary ammonium salts or cation surface-active agents.
  • development progress improving agents such as 3-pyrazolidone derivatives or pyrazolone derivatives.
  • development accelerating agents such as quaternary ammonium salts or cation surface-active agents.
  • the supports which are coated with the compounds of the present invention can be varied widely, and glass, cellulose acetate, polystyrene, polycarbonate, polyethyleneterephthalate and the like can be used.
  • EXAMPLE 1 After photographing an exposure wedge for sensitometry, through a 150-line magenta contact screen, using a commerical lithographic film comprising a film support having coated thereon a silver chlorobromoiodide emulsion (70 mol% AgCl, 0.2 mol% Agl) sensitized with gold and sulfur, spectrally sensitized with 3- carboxymethyl-S 2-( 3-ethylthiazolinilidene) ethylidene) rhodamine, and containing polyoxyethylenenonylphenyl ether having 50 ethyleneoxide groups, muccochloric acid and polybutylmethacrylate, development was conducted at 20C using four kinds of developing solutions having the following compositions:
  • Developing Solution A Sodium Carbonate (monohydrate)50 g Formaldehyde-Sodium Bisulfite Adduct45 g Potassium Bromide-2 g Hydroquinone18 g Sodium Sulfite-2 g Water to makel liter Developing Solution B Developing Solution B was prepared by adding 10 g of Compound-1 of the present invention to Developing Solution A.
  • Developing Solution C Developing Solution C was prepared by adding additionally 3 g of sodium sulfite to Developing Solution A.
  • Developing Solution D Developing Solution D was prepared by adding 1.0 g of ascorbic acid to Developing Solution A.
  • the development time is expressed as the time required to reach the sensitivity obtained when development was conducted for 2 minutes using Developing Solution A, this sensitivity being set at 100.
  • the dot quality was graded as a, b, c, each representing good, fairly good" and bad, respectively.
  • the aerated sensitivity was obtained by placing 500 ml of developing solution in a cm X cm developing bath and contacting such with air for 5 hours to determine deterioration.
  • 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 not completely satisfactory.
  • Developing Solution B containing 10 g of Compound-1 of the present invention shows the smallest decrease in sensitivity when aerated, and no decrease in the dot quality was observed at all.
  • EXAMPLE 2 as described in Japanese application 23 ,465/65, mucochloric acid, polybutylmethacrylate prepared by emulsion polymerization as described in Japanese application 5,331/70 and pentaerythritol. The mixture was then coated on a film base to manufacture the desired lithographic film.
  • Developing Solution G Sodium Carbonate (monohydrate)55 g Formaldehyde-Sodium Bisulfite Adduct-6O g Potassium Bromide-2 g Boric Acid-3 g Hydroquinone18 g Sodium Sulfite2 g Water to makel liter
  • the Developing Solutions H, I, J, K, L, M were prepared by adding the Compound-Ii, -4, -5, -6, -1 1, -l3 of the present invention, respectively, to Developing Solution G.
  • EXAMPLE 4 Each of two 25 liter portions of a Developing Solution E as described in Example 2 was placed in two developing apparatus for engraving. 200 sheets of a halfcut lithographic film were processed in each, with 70 ml of a supplementary solution of the following composition being added for each sheet of the half-cut lithographic film.
  • Supplementary Solution Solution 1 Distilled Water45 ml Triethylene Glycol-40 ml Formaldehyde-Sodium Bisulfite Adduct-45 g Hydroquinonel 8 g Distilled Water to make-125 ml Solution 2 Distilled Water-9O ml Sodium Carbonate (monohydrate)-3O g Sodium Hydroxide-5 g Potassium Bromide-2 g Distilled Water to make-125 ml
  • the supplementary solution was prepared by adding Solution 1 and Solution 2, in order, to 750 ml of water.
  • To one of the automatic developing apparatus was added 20 g of Compound-9 of the present invention, and both apparatus were allowed to stand for 64 hours. Then, lithographic films were developed in each automatic development apparatus. No decrease in sensitivity was observed in the automatic developing apparatus to which the compound of the present invention had been added. On the other hand, a great decrease in sensitivity was observed in the automatic developing apparatus to which no compound of the present invention had been added.
  • the aerated solution in Table 4 comprises a developing solution which has been allowed to stand at room temperature for 64 hours in an automatic developing apparatus. From the results it can be seen that no deterioration of the dot quality occurs and a remarkably excellent stability is obtained with the developing solutions containing Compound-3, -4, -5, -6, -11 or -l3 of the present invention.
  • R R and R which may be the same or different, each represents a hydrogen atom, an alkyl group with not more than four carbon atoms, a halogensubstituted alkyl group with not more than four carbon atoms, an alkoxy group with not more than four carbon atoms, a COOM group in which M represents a hydrogen atom or a water-soluble cation, a COR group in which R represents an alkyl group with not more than 4 carbon atoms, a CONRR" group in which R and R each represents a hydrogen atom or an alkyl group with not more than four carbon atoms or CN, and n represents 0 or an integer of from 1 to 3.
  • composition of claim 1 wherein said composition additionally contains an aldehydealkali metal bisulfite adduct, a ketone-alkali metal bisulfite adduct or a combination thereof.
  • dihydroxy developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, or 2, S-dimethylhydroquinone.
  • R is a hydrogen atom, a ,carboxyl group, or a cyano group, and wherein R and R are hydrogen atoms.
  • a method for forming photographic images for the graphic arts which comprises exposing imagewise a high contrast photographic element having a silver chloride content not less than 50%, and developing said exposed element in a developer composition comprising a dihydroxybenzene developing agent, sulfite ion in an amount up to 5g/liter and at least one compound having the formula:
  • R R and R which may be the same or different, each represents a hydrogen atom, an alkyl group with not more than four carbon atoms, a halogen-substituted alkyl group with not more than four carbon atoms, an alkoxy group with not more than four carbon atoms, a COOM group in which M represents a hydrogen atom or a water-soluble cation, a COR group in which R represents an alkyl group with not more than four carbon atoms, a CONR'R" group in which R and R each represents a hydrogen atom or an alkyl group with not more than four carbon atoms or CN, and n represents 0 or an integer of from 1 to 3.
  • composition additionally contains an aldehyde-alkali metal bisulfite adduct, a ketone-alkali metal bisulfite adduct or a combination thereof.
  • R is a hydrogen atom, a carboxyl group, or a cyano group, and wherein R and R are hydrogen atoms.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00239978A 1971-03-31 1972-03-31 Developing composition for use with photographic materials for the graphic arts Expired - Lifetime US3772022A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP46019515A JPS519613B1 (OSRAM) 1971-03-31 1971-03-31

Publications (1)

Publication Number Publication Date
US3772022A true US3772022A (en) 1973-11-13

Family

ID=12001479

Family Applications (1)

Application Number Title Priority Date Filing Date
US00239978A Expired - Lifetime US3772022A (en) 1971-03-31 1972-03-31 Developing composition for use with photographic materials for the graphic arts

Country Status (6)

Country Link
US (1) US3772022A (OSRAM)
JP (1) JPS519613B1 (OSRAM)
DE (1) DE2215714A1 (OSRAM)
FR (1) FR2132371B1 (OSRAM)
GB (1) GB1346028A (OSRAM)
IT (1) IT952467B (OSRAM)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3841878A (en) * 1971-09-17 1974-10-15 Agfa Gevaert Nv High temperature processing of photographic silver halide elements
US4699868A (en) * 1984-03-02 1987-10-13 Minnesota Mining And Manufacturing Company Photographic tanning developer formulation

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3543291A (en) * 1967-02-17 1970-11-24 Bolls & King Photolithography

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3543291A (en) * 1967-02-17 1970-11-24 Bolls & King Photolithography

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3841878A (en) * 1971-09-17 1974-10-15 Agfa Gevaert Nv High temperature processing of photographic silver halide elements
US4699868A (en) * 1984-03-02 1987-10-13 Minnesota Mining And Manufacturing Company Photographic tanning developer formulation

Also Published As

Publication number Publication date
IT952467B (it) 1973-07-20
FR2132371B1 (OSRAM) 1976-08-13
GB1346028A (en) 1974-02-06
DE2215714A1 (de) 1972-10-05
JPS519613B1 (OSRAM) 1976-03-29
FR2132371A1 (OSRAM) 1972-11-17

Similar Documents

Publication Publication Date Title
US4298673A (en) Lithographic type diffusion transfer developing composition
US3793027A (en) Developing composition for use with photographic materials for the graphic arts
US4632896A (en) Processing solution for silver complex diffusion transfer process comprising amino alcohols
CA1110483A (en) High contrast continuous tone developer containing hydroquinone, sulfite, organic azole antifogging agent and alkanolamine
US3615440A (en) Novel photographic compositions and processes
US3658527A (en) Oxidation inhibitors for photographic materials
US3984243A (en) Photographic developer compositions for obtaining high contrast images
US3833378A (en) Developer composition for producing photographic materials for the graphic arts
AU689168C (en) Non-hydroquinone photographic developer composition and processing method
US4147543A (en) Developer compositions for high contrast diffusion transfer photographic materials and process therefor
US3573914A (en) Photographic developer composition containing carbonyl bisulfite amine condensation product and free amine
US3772022A (en) Developing composition for use with photographic materials for the graphic arts
US4022621A (en) Photographic developer composition
US3671247A (en) Development of silver halide photographic materials
DE69325335T2 (de) Verfahren zur Entwicklung schwarzweisser photographischer lichtempfindlicher Silberhalogenidmaterialien
US3578449A (en) Transfer image process utilizing an organic phosphine as silver halide solvent
US3265501A (en) Water-swellable colloidal magnesium aluminum silicate photographic composition
US3740221A (en) Development of photographic material
DE69310356T2 (de) Photographische Silberhalogenidentwicklerzusammensetzungen und Verfahren zur Herstellung von photographischen Silberbildern
US3563740A (en) Use of dicyanamides in and with photosensitive systems
US3337342A (en) Photographic developing agents
USRE29111E (en) Photographic developer composition containing formaldehyde bisulfite alkanolamine condensation product and free alkanolamine
US3276875A (en) Developing composition with pyrrolidone anti-sludging agent
US3236642A (en) Process for producing direct positives by the silver salt diffusion process
US3300307A (en) Photographic developer composition