US3876427A - Developer for photographic materials used in the graphic arts - Google Patents

Developer for photographic materials used in the graphic arts Download PDF

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Publication number
US3876427A
US3876427A US328808A US32880873A US3876427A US 3876427 A US3876427 A US 3876427A US 328808 A US328808 A US 328808A US 32880873 A US32880873 A US 32880873A US 3876427 A US3876427 A US 3876427A
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US
United States
Prior art keywords
developer
compound
sulfite
sodium
development
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
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US328808A
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English (en)
Inventor
Eiichi Okutsu
Haruhiko Iwano
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
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Publication of US3876427A publication Critical patent/US3876427A/en
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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
    • G03C5/305—Additives other than developers

Definitions

  • ABSTRACT A developer for photographic materials used in the graphic arts which has excellent preservability but no adverse influence upon image quality containing at least one compound represented by the general formula wherein R R R and R which may be the same or different, each represents H, OH, CH;, or COOM with M being a hydrogen atom. a water-soluble cation or a lower alkyl group of not more than 4 carbon atoms.
  • a photographic silver halide material has the property that it produces. in addition to maximal and minimal density portions for the formation of dot images. areas of intermediate density. so that when the combination of a high contrast photographic light-sensitive material and a standard black-and-white developer is used an area of density gradation with a density less than the dot images. that is. fringe. is produced around the images. which is not desirable in plate making.
  • Fringe can be avoided to a certain extent by using a so called infectious developer comprising a dihydroxy benzene such as hydroquinone as a developing agent in combination with sodium sulfite and paraformaldehyde.
  • a so called infectious developer comprising a dihydroxy benzene such as hydroquinone as a developing agent in combination with sodium sulfite and paraformaldehyde.
  • ascorbic acid is decomposed with ease. particularly in a developer which contains metal ions such as copper ions and iron ions. Moreover, the resulting developer is of insufficient preservability. In addition. the use of ascorbic acid presents such drawbacks that it delays development to some extent and the addition of too large a quantity thereof leads to a deterioration in dot quality.
  • one object of the invention is to provide a developer for printing photographic materials in the graphic arts field where it is desired to make photographic line and halftone reproductions. which dcvcloper has excellent preservability but no adverse influence upon image or dot quality (such materials are occasionally referred to as dot photographic materials).
  • Another object of the invention is to make it possible to manufacture a photographic printing plate which is of stable quality over a long period of time using a dcveloper having high preservability.
  • Another object ofthe invention is to simplify the handling and storing of such a developer.
  • Still another object of the invention is to reduce the make-up amounts of developer required during infectious development.
  • R R R and R which may be the same or different. each represents H. OH, CH,-; or COOM. with M being a hydrogen atom.
  • a vvatersoluble cation e.g.. ammonia or an alkali metal such as sodium or potassium. or an alkyl group having four or less carbon atoms. is added to an infectious developer the preservability of the developer is remarkably improved without any adverse influence upon dot quality.
  • Compound 1 Compound 2 Compound 3 Q a El Compound 4 Hill 011 Compound 5 CH O CH 3 U 3 Compound 6 H000 ul nj COOH 0 Compound 7 O COCH 0 Compound 8 COOCH3 Compound 9 0 cooc a
  • the compounds ofthe present invention may be used in the form of their water-soluble salts such as the potassium. sodium and ammonium salts, or salts with sulfuric acid or hydrochloric acid.
  • infectious developer denotes a developing composition essentially comprising. before use a dihydroxybenzene as a developing agent, an alkali a small amount of a sulfite and a sulfite ion buffer, the compound or compounds according to the invention being added to such a composition.
  • dihydroxybenzenes used as developing agents one may use any suitable compounds known for such purpose in the photographic arts.
  • suitable compounds include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, trihydroquinone, methylhydroquinone, 2,3- dichlorohydroquinone and 2,S-dimethylhydroquinone, of which hydroquinone is most commonly used.
  • the amount of the developing agent added can be in the range of from about 5 to about '50 grams, preferably 10 to 30 grams, per liter of developer.
  • the sulfite ion buffer is used in an amount effective to keep the sulfite present in the developer at a low concentration level.
  • sulfite ion buffers include aldehydealkali hydrogen sulfite adducts such as formaldehyde-sodium hydrogen sulfite adduct, ketone-alkali hydrogen sulfite adducts such as acetonesodium hydrogen sulfite adduct, carbonyl bisulfiteamine condensation products such as sodium bis(2- hydroxyethyl )aminomethanesulfonate and the like.
  • the sulfite ion buffer used in the invention is in no way limited to these specific examples.
  • each of the components in the adducts or condensation products may be added separately to the developer.
  • the amount of the sulfite ion buffer can range from about 13 to about grams, and preferably from 30 to 60 grams, per liter of the developer used.
  • the sulfite ion buffers are well known materials and many examples thereof are described in US. Pat. Nos. 3,294,540; 3,516,830; 3,573,914; 3,615,524; and 3,625,689.
  • An alkali is added to the developer to make the developer alkaline, more preferably to adjust the pH to 9 or more.
  • One may employ any amount or kind of alkali known to the art which is suitable for the pH adjustment purpose, e.g., sodium hydroxide, potassium hydroxide and/or sodium carbonate.
  • the amount of free sulfite is less than 5 g/l.
  • the infectious developer according to the invention may contain. if desired or needed for some special development, in addition to the components specified above a pH buffering agent such as a water soluble acid. an alkali or salt. and/or a development restrainer such an alkali halide. Certain alkalis not only make the developer alkaline but also function as a pH buffering agent and development restrainer.
  • the developer may contain an organic anti-fogging agent such as benzotriazole and l-phenyl-5-mercapto-tetrazole. a polyalkylene oxide. an amine compound and/or an organic solvent (in amounts ranging from 0 to 300 ml per liter of the developer) such as triethylene glycol. dimethyl formamide. methyl alcohol and cellosolve. With regard to the exact composition and amount of the abovementioned materials added to the infectious developer. one may use any of these components in an amount as is known in the art.
  • the compounds according to the invention may be used alone or as a mixture of two or more of such compounds.
  • the amount of the compound of the invention used is generally within the range of0.1 to 30 grams per liter of the developer used and preferably within the range of from 0.5 to grams.
  • the compounds according to the invention may be added to either composition. although it is in particular efficient to add them to the composition containing a developing agent since by the addition in this manner the preservability of the liquid developing composition and thus of the infectious developer obtained by diluting the composition are remarkedly improved.
  • Solvents for such developing compositions include any of those solvents known in the art. for example water. benzyl alcohol. ethylene glycol. diethylene glycol. triethylene glycol. glacial acetic acid or mixtures of such solvents.
  • the compounds of this invention may be added to a developer for printing photographic materials to improve the preservability of the developer used.
  • Printing light-sensitive materials which may be used in the invention include any silver halide emulsion such as silver chloride.
  • These silver halide emulsions may contain. as a dispersing agent. one or more hydrophilic colloidal substances. for example. gelatin or derivatives thereof such as gelatin modified with phthalic acid or malonic acid. cellulose derivatives such as collodion. hydroxy ethyl cellulose and carboxymethyl cellulose. soluble starches such as dextrin and alkalized starch. and hydrophilic polymers such as polyvinyl alcohol. polyvinyl pyrrolidonc. polyacrylamide and polystyrene sulfonic acid.
  • preferred emulsions are those where the silver halide grain size is (1.1 to 1 micron and which contain a preferred amount of a hydrophilic colloid material such as gelatin in an amount of 30 to g per l mol of silver halide.
  • the silver halide emulsions may also contain hydrophobic polymers such as polyalkyl acrylates. polymethacrylates. polyacrylic acid and copolymers of an alkyl acrylate and acrylic acid. or gelatinplasticizers such as glycerin trimethanolpropane.
  • hydrophobic polymers such as polyalkyl acrylates. polymethacrylates. polyacrylic acid and copolymers of an alkyl acrylate and acrylic acid. or gelatinplasticizers such as glycerin trimethanolpropane.
  • the emulsions used in the light-sensitive materials can be. when they are prepared or applied. sensitized by varied methods. For example. they may be chemically sensitized in various manners known to the art. for example by using sodium thiosulfate. alkyl thiourea or like sulfur-containing compounds. and/or a compound of gold such as a complex of an aurous compound and thiocyanic acid. They may also contain compounds of a heavy metal such as platinum, palladium. iridium. rhodium. cadmium or the like. Alternatively. they may be orthochromatically or panchromatically sensitized by adding a color sensitizer such as a cyanine dye or a merocyanine dye thereto.
  • a color sensitizer such as a cyanine dye or a merocyanine dye thereto.
  • the emulsions may contain dot quality-improving agents such as polyalkylene oxides and amine compounds (see Japanese Pat. Publication 14.402/64. which is the equivalent of U.S. Pat. No. 3.288.612. German Patent Application Laid Open to Public lnspection No. 1. 932. 882. Japanese Pat. Publication 23.466/65. equivalent to U.S. Pat. No. 3.345.175). sodium benzene thiosulfate and benzotriazole or 1. 3 3a. 7-tetrazaindene derivatives (see Japanese Patent Publication No. 15.715/64, equivalent to U.S. Pat. No. 3.375.114. and Japanese Patent Publication 17.903).
  • dot quality-improving agents such as polyalkylene oxides and amine compounds (see Japanese Pat. Publication 14.402/64. which is the equivalent of U.S. Pat. No. 3.288.612. German Patent Application Laid Open to Public lnspection No. 1. 932. 882
  • ком ⁇ онентs may also be hardened with a hardener such as formaldehyde. dimethylol urea. 2.. 4-dichloro-6-hydroxy- 1. 3. S-triazine (U.S. Pat. No. 3.325.287) or mucochloric acid and may contain a surface active agent such as saponin as a coating aid. Moreover. they may include a development improver such as a 3- pyrazolidone or pyrazolone derivative. and/or a de ⁇ elopment accelerator such as a quaternary ammonium salt or a cationic surface active agent.
  • a hardener such as formaldehyde. dimethylol urea. 2.. 4-dichloro-6-hydroxy- 1. 3.
  • S-triazine (U.S. Pat. No. 3.325.287) or mucochloric acid may contain a surface active agent such as saponin as a coating aid.
  • a development improver such as a 3-
  • the support for the emulsions used in the invention may employ any suitable support known in the art. for example glass. cellulose acetate. polystyrene. polycarbonate and polyethylene telephthalate.
  • Developer A plus l g LfilStIUl'l lC acid The resulting photographic properties are shown in speed as with Developer A.
  • 'l'hc dot quality was classified into 10 equally spaced classes on a visual evaluation basis. where 10 was excellent and l was extremely poor.
  • 'lhe term "aged developer"- means 1 liter of developer placed in a l liter beaker and kept in contact with thc air by allowing the developer to stand at room temperaturc for three days.
  • EXAMPLE 2 A silver halide emulsion consisting of 75 mol 9? of silver chloride and 0.2 mole "/1 of silve iodide. remainder silver bromide. was subjected to gold-and sulfur-sensitizations followed by optical sensitization with 3- carboxymethyl-S-l2-(3- ethylthiazolinylidene)ethylidene] rhodamine. To the sensitized emulsion were added a polyoxyethylene bearing ethylene oxide groups. nonyl phenyl ether, a development accelerator as described in Japanese Patent Publication 23465/ (of the formula N-CH 2CH2CH2CH-NHCONH l 2 5 on and mucochloric acid.
  • sensitometry was 50 lable 1. performed by exposing the film to a sensitometric opti- Table l Deieloper Additive Amount .'l ilnc of Dot quality Relative in g l Development Speed in min.
  • Developer E Solution [1 Distilled water 60 ml. Triethylcne glycol 35 ml. Formaldehyde-sodium hydrogen sulfitc adduct 40 g. Hydroquinone 18 g. Sodium sulfitc 3 g. Distilled water to make 125 ml. Solution ll: Distilled water 80 ml. Potassium carbonate 30 g. Sodium hydroxide 3 g. Boric acid 3 g. Distilled water to make I25 ml.
  • Solution l was added to 750 ml water and then Solution ll added to make 1 liter of developer ready for use.
  • Solution 1 was added to 666 ml of water and then Solution II was added to make 1 liter of developer ready for use.
  • lithofilm was developed using each of the two automatic developing machines to find, in the case of the developing machine to which the compound of the invention had been added, no reduction in relative speed but, in the case of the other developing machine, a marked reduction in relative speed.
  • R R R and R which may be the same or different. each represents H, OH. CH;, or COOM, with M being a hydrogen atom, a water-soluble cation or lower alkyl group of not more than 4 carbon atoms.
  • An infectious deYeloper f photogrhphic materi 5 The developer as claimed in claim 1 where the 211s used I the g p arts F P l a hydro compound(s) is present in an amount of0.l 30 g. per qumone developing agent, an alkali, a sulfite and a sulliter f developer ft bff,th' tff lft b' l e u er 6 dmoun 0 Tee Su 1 e present emg 6.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US328808A 1972-02-08 1973-02-01 Developer for photographic materials used in the graphic arts Expired - Lifetime US3876427A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP47013778A JPS4882901A (enrdf_load_stackoverflow) 1972-02-08 1972-02-08

Publications (1)

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US3876427A true US3876427A (en) 1975-04-08

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US (1) US3876427A (enrdf_load_stackoverflow)
JP (1) JPS4882901A (enrdf_load_stackoverflow)
DE (1) DE2305977A1 (enrdf_load_stackoverflow)
GB (1) GB1367604A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4619886A (en) * 1984-03-23 1986-10-28 Fuji Photo Film Co., Ltd. Process for forming high contrast negative image
US5342741A (en) * 1992-07-10 1994-08-30 Fuji Photo Film Co., Ltd. Method of processing silver halide photographic material and composition for processing

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2845349A (en) * 1955-09-07 1958-07-29 Powers Chemco Inc Photographic developers
US3382071A (en) * 1964-06-24 1968-05-07 Du Pont Silver halide photographic element containing spot or streak prevention compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2845349A (en) * 1955-09-07 1958-07-29 Powers Chemco Inc Photographic developers
US3382071A (en) * 1964-06-24 1968-05-07 Du Pont Silver halide photographic element containing spot or streak prevention compounds

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4619886A (en) * 1984-03-23 1986-10-28 Fuji Photo Film Co., Ltd. Process for forming high contrast negative image
US5342741A (en) * 1992-07-10 1994-08-30 Fuji Photo Film Co., Ltd. Method of processing silver halide photographic material and composition for processing

Also Published As

Publication number Publication date
DE2305977A1 (de) 1973-08-16
JPS4882901A (enrdf_load_stackoverflow) 1973-11-06
GB1367604A (en) 1974-09-18

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