EP0331319A1 - Méthode pour la formation d'images - Google Patents

Méthode pour la formation d'images Download PDF

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Publication number
EP0331319A1
EP0331319A1 EP89301610A EP89301610A EP0331319A1 EP 0331319 A1 EP0331319 A1 EP 0331319A1 EP 89301610 A EP89301610 A EP 89301610A EP 89301610 A EP89301610 A EP 89301610A EP 0331319 A1 EP0331319 A1 EP 0331319A1
Authority
EP
European Patent Office
Prior art keywords
group
hydrogen atom
photographic material
formula
isothiazolinone
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.)
Granted
Application number
EP89301610A
Other languages
German (de)
English (en)
Other versions
EP0331319B1 (fr
Inventor
Yasunori Wada
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.)
Konica Minolta Inc
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Konica Minolta Inc
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Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0331319A1 publication Critical patent/EP0331319A1/fr
Application granted granted Critical
Publication of EP0331319B1 publication Critical patent/EP0331319B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/37—Antiseptic agents

Definitions

  • the present invention relates to a method for the forma­tion of images which is capable of rapid processing and improv­ed so as not to cause troubles such as roller transfer marks.
  • the automatic processor it is advantageous also for the automatic processor to speed up the processing of X-ray films. For example, even if the processor is a compact-type automatic processor, if its processing speed is increased, its processing capacity per unit time then increases, while if its processing capacity need not be increased, then the processor can be of an even smaller size, thus contributing to space-saving.
  • the rapid processing requires an increased film-­transport speed.
  • an automatic processor e.g., a roller-transport-type automatic processor
  • it tends to cause such troubles as roller transfer marks appear­ing on the surface of processed film.
  • gelatin fragments from the section of the leading end or trailing end of the film being processed are attached onto transport rollers, and the gelatin fragments are then transferred from the rollers onto the surface of the subsequent film, whereby the fragments appear in the form of linear stain marks in the roller transport direction.
  • R1 represents a hydrogen atom or a straight-chain or branched-chain alkyl, cycloalkyl, alkenyl, aralkyl, aryl, heterocyclic, alkylamido, arylamido, alkylthioamido, arylthio­amido, alkylsulfoamido or arylsulfoamido group
  • R2 and R3 each represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, an alkylthio group, an arylthio group, an alkylsulfoxido group, an alkylsulfonyl group or a heterocyclic group, provided that the above alkyl, cycloalkyl, alkenyl
  • the ring to be formed by both R2 and R3 may be an aromatic ring.
  • R4 represents a hydrogen atom, a lower alkyl group having from 1 to 4 carbon atoms or a hydroxymethyl group
  • R5 represents a hydrogen atom or a lower alkyl group having from 1 to 4 carbon atoms; provided that the above-mentioned groups for R4 and R5 may independently have a substituent.
  • R6 represents a hydrogen atom, an alkyl group or an alkoxy group
  • R7, R8 and R9 each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group or a nitro group
  • R10 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a -CONHR13 group (wherein R13 is an alkyl, aryl, alkylthio, arylthio, alkylsulfonyl or arylsulfonyl group) or a heterocyclic group
  • R11 and R12 each represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a
  • Benzoisothiazoline-3-one 2-methyl-benzoisothiazoline-3-one, 2-­ethyl-benzoisothiazoline-3-one, 2-(n-propyl)-benzoisothiazol­ine-3-one, 2-(n-butyl)-benzoisothiazoline-3-one, 2-(sec-butyl)-­benzoisothiazoline-3-one, 2-(t-butyl)-benzoisothiazoline-3-­one, 2-methoxy-benzoisothiazoline-3-one, 2-ethoxy-benzoisothia­zoline-3-one, 2(n-propyloxy)-benzoisothiazoline-3-one, 2-(but­yloxy)-benzoisothiazoline-3-one, 5-chloro-benzoisothiazoline-­3-one, 5-methyl-benzoisothiazoline-3-one, 6-ethoxy-benzoiso­thiazoline-3-one, 6-cyano
  • the number of carbon atoms of each of the alkyl group and alkenyl group is 1 to 36, and more preferably 1 to 18.
  • the number of carbon atoms of the cyclo­alkyl group is 3 to 12, and more preferably 3 to 6.
  • Each of the alkyl, cycloalkyl, alkenyl, aralkyl, aryl and heterocyclic groups represented by the R10 may have a substituent which may be selected from among halogen atoms and groups including nitro, cyano, thiocyano, aryl, alkoxy, aryloxy, carboxy, sulfoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxy­carbonyl, sulfo, acyloxy, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, thioureido, urethane, thiourethane, sulfonamido, heterocyclic, arylsulfonyloxy, alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio
  • the number of carbon atoms of the alkyl group represented by the R11 or R12 is 1 to 18, and more preferably 1 to 9, and that of the cycloalkyl group repre­sented by the same is 3 to 18, and more preferably 3 to 6.
  • Each of these groups represented by the R11 or R12 may have a substituent, which is, for example, a halogen atom or a nitro, sulfo, aryl, hydroxy or the like group.
  • any of these 1,2-benzoisothiazoline-3-one compounds of Formula [III] to be used in this invention is contained in said photographic material in a proportion of 1x10 ⁇ 5 to 10% by weight relative to the total amount of hydrophilic colloid contained in the photographic material, and particularly preferably from 1x10 ⁇ 4 to 1% by weight relative to the total amount of hydrophilic colloid contained in the photographic material.
  • any of these isothiazoline-3-one compounds of Formula [IV] is contain in said photographic material in a proportion of preferably from 1x10 ⁇ 4 to 10% by weight relative to the total amount of hydrophilic colloid contained in the photographic material, and particularly preferably from 3x10 ⁇ 4 to 1% by weight relative to the total amount of hydrophilic colloid contained in the photographic material. It goes without saying that the adding amount of these compounds is allowed to be outside the range mentioned above, depending on the kind of the light-sensitive material to be used, the layer to which the compound is to be added, coating method, and the like.
  • any of these compounds may be dissolved into water or a solvent, not adversely affecting photographic characteristics, out of organic solvents including alcohols such as methanol, ethanol, isopropanol, etc., ketones such as acetone, glycols such as ethylene glycol, propylene glycol, etc., esters such as ethyl acetate, and the like, and the solution may be added to a hydrophilic colloid, may be coated on the protective layer, or may be incorporated into a photographic light-sensi­tive material in the manner of immersing the photographic light-sensitive material into the solution.
  • organic solvents including alcohols such as methanol, ethanol, isopropanol, etc., ketones such as acetone, glycols such as ethylene glycol, propylene glycol, etc., esters such as ethyl acetate, and the like
  • the solution may be added to a hydrophilic colloid, may be coated on the protective layer, or may be incorporated into a
  • the compound may be dissolved into a high-boiling solvent, a low-boiling solvent or a mixture of these solvents, then emulsifiedly dispersed in the presence of a surface active agent, and then added to a liquid containing a hydrophilic colloid or coated over the protective layer.
  • the compound may be incorporated into a high-polymer compound such as butyl polyacrylate, then dispersed in the presence of a surface active agent, and the dispersed liquid is then added to a liquid containing a hydrophilic colloid or coated over the protective layer.
  • the above l can be found on the basis of, e.g., a light-­sensitive material comprising a 175 ⁇ m-thick polyethylene terephthalate support having photographic component layers thereon.
  • T implies the whole period of time the leading end of a sheet of film takes to travel from the insertion of it in the first roller at the film inlet, passing through the developer bath, crossover section, fixer bath, crossover section, wash water bath, crossover section and drying sec­tion, until the ejection of it from the final roller at the film outlet in the drying section of an automatic processor; in other words, the quotient (sec.) obtained by dividing the whole length (in meters) of the processing line by the line transport speed (meters/sec.).
  • crossover section passage time is included, well-known to those skilled in the art, is that even in the crossover section, substantial processing is considered to be still going on due to the preceding process' liquid contained in the swelled gelatin layer of the film in transit.
  • the whole number of the transport rollers of the auto­matic processor for use in the image forming method of this invention when expressed in terms of the value obtained dividing the l, the whole processing line's length of the automatic processor, by the number of the rollers, is desir­able to be in the range of from 0.01 to 0.04.
  • the processing time proportions and ranges required in the indivi­dual processing positions are desired to be as follows: Insertion + developing + crossover: 25 to 40% Fixing + crossover: 12 to 25% Washing + crossover: 10 to 25% Squeeze + drying: 25 to 45% Total 100 %
  • each roller to be used in its transport-­functional part, is desirable to be 12mm to 60mm in diameter and 30cm to 110cm in length.
  • the roller may be made of various materials; for example, bakelite-type materials (allowed to contain glass powder, metal powder or plastic powder) or rubber-type materials (e.g., neoprene, isoprene, silicone rubber) may be used for the rollers in the develop­ing, fixing, washing and drying sections, and repellent and elastic silicone rubber or highly water-absorbing synthetic leather such as the commercial product called 'Kurarino' (Kuraray Co., Ltd.) may be preferably used for the rollers in the crossover and squeeze sections.
  • bakelite-type materials allowed to contain glass powder, metal powder or plastic powder
  • rubber-type materials e.g., neoprene, isoprene, silicone rubber
  • repellent and elastic silicone rubber or highly water-absorbing synthetic leather such as the commercial product called 'Kurarino' (Kuraray Co., Ltd
  • the above l is in the range of from 0.7m to 3.1m, whereby satisfactory results can be obtained. If the l is less than 0.7m, the individual processes become small with the number of the rollers to be used being reduced, thus deteriorating the sensitivity of or affecting the transpor­tability of the light-sensitive material being processed. On the contrary, if the l is larger than 3.1m, the transport speed is increased to excess, whereby not only is the film liable to get scratched but the durability of the automatic processor is abruptly deteriorated.
  • the sensi­tivity of the film in processing is abruptly lowered, and besides, in a film containing not less than 10mg/m2 of a sensitizing dye per side of its support, the residual dye stain also becomes a problem.
  • the product of l 0.75 and T should be not less than 76.
  • Typical additives to be added to the developer solution include an antifoggant; a development accelerator comprised of an alkali agent such as sodium hydroxide, sodium carbonate, potassium carbonate, etc.; an inorganic or organic restrainer such as potassium bromide, 2-methylbenzimidazole, methylbenzo­thiazole, etc.; a water softener such as a polyphosphate; and an anti-surface-overdevelopement agent comprising a slight amount of an iodide or mercapto compound.
  • a development accelerator comprised of an alkali agent such as sodium hydroxide, sodium carbonate, potassium carbonate, etc.
  • an inorganic or organic restrainer such as potassium bromide, 2-methylbenzimidazole, methylbenzo­thiazole, etc.
  • a water softener such as a polyphosphate
  • an anti-surface-overdevelopement agent comprising a slight amount of an iodide or mercapto compound.
  • a preservative such as a sulfite; a buffer such as a carbonate, boric acid, a borate, an alkanolamine, etc.; an alkali agent such as a hydroxide, a carbonate, etc.; a dissolv­ing aid such as polyethylene glycol or an ester thereof; a pH control agent comprised of an organic acid such as acetic acid; a sensitizer such as a quaternary ammonium salt; a surface active agent, and the like, may be used.
  • the developer solution may contain a hardening agent.
  • a hardening agent a dialdehyde-type hardening agent may be suitably used.
  • the developer solution may also contain a chelating agent such as, e.g., ethylenediaminetetraacetic acid or an alkali metal salt thereof, a polyphosphate or a nitriloacetate.
  • a chelating agent such as, e.g., ethylenediaminetetraacetic acid or an alkali metal salt thereof, a polyphosphate or a nitriloacetate.
  • the developing temperature is generally determined in connection with developing time.
  • the developing temperature and developing time are preferably, e.g., 30 to 40°C and 6 to 20 seconds, respectively.
  • the fixer bath to be used in the fixing process of this invention is an aqueous solution containing, e.g., a thio­sulfate and a water-soluble aluminum compound, and the solu­tion may also contain a polybasic acid such as citric acid, tartaric acid or the like, and its pH is preferably about 3.5 to 5.0 (at 20°C).
  • the developing process may be followed by a stop process.
  • the stop process is excluded from general roller-transport-type automatic processors, so that part of the developer solution is carried out into the fixer solution, whereby the pH of the fixer solution may sometimes be raised. For this reason, the pH of the fixer solution is desirable to be adjusted to about 3.6 to 4.7 (at 20°C).
  • a thiosulfate such as ammonium thiosulfate, sodium thiosulfate or the like is generally used.
  • ammonium thiosulfate is particularly suitably used from the fixing speed point of view.
  • the using amount of the fixing agent although allowed to be arbitrarily varied, is normally from about 0.1 to 5 moles per liter.
  • a water-soluble aluminum salt may be used which functions principally as a hardening agent in the fixer solution.
  • This is a compound which is generally known as the hardening agent for acid hardening fixing solutions, and examples of it include, e.g., aluminum chloride, aluminum sulfate, potassium alum, and the like.
  • the fixing temperature and time in this invention are preferably, e.g., 20° to 35°C and 4 to 15 seconds, respectively.
  • a photographic material that has been developed and fixed is generally washed and then dried.
  • the washing takes place in order to almost completely remove the silver salt that has been dissolved by fixing, and is desirable to take place for a period of about 5 to 12 seconds at about 20° to 50°C.
  • the drying is to take place at a temperature of about 40° to 100°C for an appropriate period of time.
  • the drying time although allowed to be arbitrarily varied according to ambient condi­tions, is normally from about 5 to 15 seconds.
  • roller-transport-type automatic processor suitably usable in practicing this invention are given in Figure 1 and Figure 2.
  • 1 is the first roller at the film inlet in the insertion section
  • 2 is the final roller at the film outlet in the drying section
  • 3a is a developer bath
  • 3b is a fixer bath
  • 3c is a wash water bath
  • 4 is a light-­sensitive material to be processed
  • 5 is a squeegee section
  • 6 is a drying section
  • 7 is a drying air outlet port.
  • a silver iodobromide emulsion of which the average silver iodide content is 2.0 mole% was subjected to gold-sulfur sensitization by using a chloroaurate, sodium thiosulfate and ammonium thiocyanate, stabilized by using 4-hydroxy-6-methyl-­1,3,3a,7-tetrazaindene, and spectrally sensitized by using the following Sensitizing Dyes A and B:
  • an emulsion liquid (silver halide coating liquid).
  • the following adding amounts are values per mole of silver halide.
  • a protective layer coating liquid containing matting agents comprised of 1g/liter of polymethyl methacrylate having an average particle size of 3.5 ⁇ m and 30g/liter of colloidal silica and the following compounds as surface active agents was prepared.
  • the thus prepared emulsion and the protective layer coating liquid were coated simultaneously, in the order of the emulsion layer and protective layer from the support side, at a coating speed of 90m/min on both sides of a 175 ⁇ m-thick polyethylene terephthalate film support, both sides of which were subbed with an aqueous copolymer-dispersed liquid obtained by diluting to 10% by weight a copolymer comprised of three different monomers: 50% by weight of glycidyl methacryl­ate, 10% by weight of methyl acrylate, and 40% by weight of butyl methacrylate, whereby samples No.1 through No.33 were obtained.
  • the coating weight of silver of each sample was 40mg/dm2.
  • the gelatin coating weight of the emulsion layer was 2.0g/m2, and that of the protective layer was 1.0g/m2.
  • the gelatin that was used in each layer was lime-treated Osein gelatin.
  • each sample was cut into pieces by the cutting machine shown in Figure 3, wherein A1 and A2 indicate cutting blades, and B indicates a light-sensitive material (sample). Evaluation of the roller transfer marks on each sample was made by expressing in terms of the difference ⁇ D between the densities, measured by an automatic densitometer, of the roller transfer marks and of their ambient areas.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photographic Processing Devices Using Wet Methods (AREA)
EP89301610A 1988-02-20 1989-02-20 Méthode pour la formation d'images Expired - Lifetime EP0331319B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP37717/88 1988-02-20
JP63037717A JP2613415B2 (ja) 1988-02-20 1988-02-20 画像形成方法

Publications (2)

Publication Number Publication Date
EP0331319A1 true EP0331319A1 (fr) 1989-09-06
EP0331319B1 EP0331319B1 (fr) 1994-01-26

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EP89301610A Expired - Lifetime EP0331319B1 (fr) 1988-02-20 1989-02-20 Méthode pour la formation d'images

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EP (1) EP0331319B1 (fr)
JP (1) JP2613415B2 (fr)
DE (1) DE68912619T2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6187526B1 (en) 1998-12-03 2001-02-13 Eastman Kodak Company Method to prevent the growth of micro-organisms in photographic dispersions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040009440A1 (en) 2002-07-11 2004-01-15 Alice Moon Coating composition for photographic materials

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2002530A (en) * 1977-08-03 1979-02-21 Fuji Photo Film Co Ltd Preservation of a solution of a hydrophilic colloid containing a viscosity-increasing agent
EP0308212A2 (fr) * 1987-09-15 1989-03-22 Konica Corporation Méthode de traitement d'un matériau photographique à l'halogénure d'argent sensible à la lumière et machine de traitement automatique à cet effet

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59226343A (ja) * 1983-06-07 1984-12-19 Konishiroku Photo Ind Co Ltd 写真用コロイド銀水性組成物の防腐方法
JPS60119547A (ja) * 1983-12-01 1985-06-27 Konishiroku Photo Ind Co Ltd 写真用水性分散液組成物の防腐方法
JPS62105138A (ja) * 1985-10-31 1987-05-15 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料の処理方法
JP2530145B2 (ja) * 1986-03-13 1996-09-04 コニカ株式会社 ハロゲン化銀写真感光材料及びその処理方法
EP0316864A3 (fr) * 1987-11-17 1990-05-09 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière et procédé de traitement

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2002530A (en) * 1977-08-03 1979-02-21 Fuji Photo Film Co Ltd Preservation of a solution of a hydrophilic colloid containing a viscosity-increasing agent
EP0308212A2 (fr) * 1987-09-15 1989-03-22 Konica Corporation Méthode de traitement d'un matériau photographique à l'halogénure d'argent sensible à la lumière et machine de traitement automatique à cet effet

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
AGFA-GEVAERT N.V., advertising material "Rapiline 95", no. 21.5748, July 1985, 4 pages, Mortsel, BE *
AGFA-GEVAERT N.V., advertising material "Scopix 12", no. MR/681/3215, June 1981, 6 pages, Mortsel, BE *
PATENT ABSTRACTS OF JAPAN, vol. 8, no. 275 (P-321)[1712], 15th December 1984; & JP-A-59 142 543 (KONISHIROKU SHASHIN KOGYO K.K.) 15-08-1984 *
PATENT ABSTRACTS OF JAPAN, vol. 9, no. 273 (P-401)[1996], 30th October 1985; & JP-A-60 119 547 (KONISHIROKU SHASHIN KOGYO K.K.) 27-06-1985 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6187526B1 (en) 1998-12-03 2001-02-13 Eastman Kodak Company Method to prevent the growth of micro-organisms in photographic dispersions

Also Published As

Publication number Publication date
JP2613415B2 (ja) 1997-05-28
DE68912619T2 (de) 1994-05-26
DE68912619D1 (de) 1994-03-10
EP0331319B1 (fr) 1994-01-26
JPH01213659A (ja) 1989-08-28

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