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
• • 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
  • G03C1/30—Hardeners
  • G03C1/301—Aldehydes or derivatives thereof, e.g. bisulfite addition products
• • 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
  • G03C5/268—Processing baths not provided for elsewhere, e.g. pre-treatment, stop, intermediate or rinse baths

Definitions

• the present invention relates to a process for hardening emulsion layers for silver halide photographic light-sensitive elements.
• a silver halide photographic light-sensitive element When a silver halide photographic light-sensitive element is processed at high temperature or it is processed for a long time in solutions of high pH, as is the case with the processing of reversal color photographic materials, it is necessary to harden the emulsion layers thereof at an early stage of the processing to prevent the emulsion layers from being damaged during the processing.
• the examples of such hardening process are the treatment of photographic materials with an aqueous alkaline solution of an aliphatic aldehyde or with an aqueous solution of aluminium sulfates.
• the hardening solution should harden emulsion layers effectively without giving chemical fogs to the emulsions.
• Aldehydes often give fogs to silver halide emulsions owing to' their reducing property, therefore, for hardening it is important to overcome such a difliculty.
• the hardening solution should afford the quick hardening. That is, the emulsion layers should be hardened within one minute in a pre-hardening bath, or when the hardeners are in developers, they should be hardened quickly at the beginning of the development.
• the suflicient hardening should be attained by possibly small content of hardening agent in solution.
• the benefit of reducing hte concentration of hardening agents lies not only in decrease in chemical cost but also in elimination of their undesirable secondary effects and the easier scavenging of residual hardening agents after the prehardening process.
• a large quantity of an aldehyde is necessary for the hardening at low pH. To reduce the aldehyde concentration, the pH of the bath must be increased,
• an improved hardening agent should have a suflicient hardening effect even in solution of low concentration and low pH.
• the hardening agent should not react with colorforming materials (couplers) in the emulsion layers.
• an object of the present invention is to provide a hardening process for photographic light-sensitive elements capable of performing effective hardening without accompanying the aforesaid technical difliculties.
• an object of the present invention is to provide a hardening process for photographic light-sensitive elements capable of exhibiting effectively the hardening effect even at a low concentration of hardening agent in a very short period of time with less formation of fogs and without accompanying undesirable reaction with couplers.
• Another object of this invention is to provide a hardening agent capable of being used not only in hardening bath but also in a hardening developer by which hardening is proceeded simultaneously with the course of development.
• R CHO wherein R and R each represents a hydrogen atom, a lower alkyl group such as a methyl group or an ethyl group, a group capable of increasing water-solubility, such as -SO H, COOH, or -OH, Na, K or NH, salt thereof.
• Phthalaldehyde OHO (2) Isophthalaldehyde (4) 2-methylterephthalaldehyde CHO I @CH] l O HO 3 (5) 4,5-dimethylphthala1dehyde (6) 4-hydroxyphthalaldehyde (7) S-methylisophthalaldehyde CHO C CHO (8) Z-hydroxyisophthalaldehyde (9) 4 hydroxyisophthalaldehyde (10) 2,4-dihydroxyisophthalaldehyde III H (1 1) 4,6-dihydroxyisophthalaldehyde 0- O m QM 4.. o
• an additive amount of formaldehyde is 5-30 ml. of a 37% aqueous solution per one liter of the processing solution, preferably 20 ml. of a 37% aqueous solution.
• Japanese patent publication No. 27,560/64 discloses a process of hardening by a mixture of the abovementioned dialdehyde and formalin is excellent on the 7 point of less fog formation as compared vvith the, known combination of aldehydes. Furthermore,thewconibination of this invention is more profitable, because .the solution,
• the hardening agent of this invention can be used not only for pre-harclener but also for a devel oper to enable simultaneous hardening and development intonev processing 'bath without much increase in developer tog.
• composition A 5.4 ml. of sulfuric acid (1:1), 150 g. of sodium sulfate and 20 g. of sodium acetate;
• composition B 5.4 ml. of sulfuric acid, 150 g. of sodium sulfate,
• composition C 20 g. of sodium acetate, and 20 ml. of formalin (37%); composition C: 5.4 ml. of sulfuric acid, ,150 g..of sodium sulfate, 20 g. of sodium acetate, 1.0g. of phthaldialde hyde; composition D:- 4 ml. of sulfuric. acid, 150 g of sodium sulfate, g. of sodium acetate, and 1.0 g. of isoph: thalaldehyde; composition E: 5.4 ml. .of sulfuric acid, 15.0 g. of sodium sulfate, 20g. of sodium acetate and 1,0 g.
• composition F 5 .4 ml. of sulfuric acid, 150 .g. of sodium sulfate, 20 g. of sodium acetate, 1.0 g. of phthaldialdehyde, and 20 ml. of formalin (37%); composi: tion G: 5.4. ml. of sulfuric acid, 150 g. of sodium sulfate, 20 g. of sodium acetate,. l,0 g. of isophthalaldehyde,,20 ml. of formalin (37%); compositionHpSAnil. of sulfuric acid, 150 g.” of sodium sulfate, 20 g. of sodium acetate, 1.0 g.
• composition 1 5.4 ml. of sulfuric acid (1:1), 150 g. of so dium sulfate, 20 g. of sodium acetate, 1.0 g; of 4-hydroxyphthalaldehyde and 20 cc. of formalin (37%);
• composition I 5.4 ml. of sulfuric acid (1:1), 150 g. of sodium sulfate, 20 g. of sodium acetate, 1.0 g. of 4-hydroxy-5-methf ylisophthalaldehyde and 20 cc. of formalin (37%);
• composition K 5.4 ml. of sulfuric acid (1:1), .150 g.
• composition L 5.4 ml. of sulfuric acid, 150 -g'-. of sodium sulfate; 20 g. of sodium acetate, 1.0"g.of 2,S-dicarboxyterephthalaldea 'hyde and 20 cc. of formalin (37%); ompos-ition M:5.f1 ml. of sulfuric acid (1:1), 150'1g.;"of sodium sulfate, 20g, of sodium acetate, 1.0 g. ofj4-sulphoisoplith-alaldehyde and 20 cc. of formalin (37%).
• i I L 'Each of the compositions wasdiluted with water to one liter in volume, the pH of which was 4.8.
• the developer was a conventional blacl; and white developer for positive film containing metol and hydr' oquinone and the fixing solution was a conventional acid hardener fixer.
• the fog densities of the black and white t 1 e'gative' image thus obtained are shown in the following table.
• the melting point of the emulsion layers thus processed were measured for, knowing the ex,- tent of the hardness of the emulsion layers, the results of which are also shownin the same table.
• This valiie is the temperature when after washing the film subjectedflto the hardening processing with water, the emulsion layer was swelled and dissolved in the solution in the case of heating the film to the temperature in an aqueous 0.2 N sodium hydroxide solution.
• composition of the hardening bath was the same in Example 1.
• Other compositions for the above-mentioned processings are shown below.
• composition for the 1st developer G N-methyl-p-aminophenol sulfate 2.0 Sodium sulfite 90.0 Hydroquinone 8.0 Sodium carbonate (monohydrate) 52.5 'Potassium bromide 5.0 Potassium thiocyanate 1.0 Water to make 1 liter.
• composition for the 2nd developer Benzyl alcohol ml 5.0 Sodium sulfite g 5.0 3-methy1- 4 amino-N-ethyl N methane sul-fonamide ethyl-aniline sulfate g 1.5 Potassium 'bromide g 1 Sodium phosphate, tribasic g 30 Sodium hydroxide g 0.5 Ethylenediamine (aq. soln.) ml.. 7
• the photographic properties of the reversal color images thus obtained are shown in the following table. As shown in the results, the photographic properties .were not deteriorated. as compared with-those obtained without using the dialdehyde and also in someof them, themaxi mum density was increased. Also, the strength of. the emulsion layers processed in accordance with the present invention was very excellent as shown in Example 4.
• the processes were. carried out at C.
• the composition of the developer was as follows, .while the fixing solution was a usual acid fixing solution. 1
• composition for the developer A N-methyl-p-aminophenol sulfate, g 4. 5 4. 5 Sodium carbonate (monohydrate), g.. 41 41 Sodium sulfite, g 15 15 Hydroquinone, g...v 8. 0 8. 0 Potassium bromide, 3. 0 3. O fi -nitrobenziurldazole, g 0. 1 0.1 Formaldehyde (37%) ml- 2 2-methyl-terephthalaidehyde, g 0. 5 Sodium hydroxide;g- Y r r H 0. 1 0.1 1 Sodium sulfate, 2 4
• the processings were conducted in an automatic developing machine with 'stirring vigorously. After the processings; the formation of mechanical damage to the sur'-' face of-the emulsion layer was detected. This showed that the damage in the case of using hardening solution A was reduced to A of the damage in the case of using hardening solution B. The fog density was 0.10 in both cases.
• said aromatic dialdehyde capable of maintaining a group capable of increasing water solubility on the aromatic nucleus, said group being a member selected from the group consisting of SO H, COOH, OH, and the Na, K, or NH salt thereof.
• dialdehyde is 0.5-1.5 g. per 20 ml. of an aqueous solution of formaldehyde when the'concentration of the formaldehyde solution is about 37 by weight.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (1)

Publications (1)

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Family Applications (1)

Country Status (5)

Cited By (4)

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• 1969
  • 1969-04-17 DE DE19691919603 patent/DE1919603A1/de active Pending
  • 1969-04-17 FR FR6911951A patent/FR2006527A1/fr not_active Withdrawn
  • 1969-04-17 BE BE731638D patent/BE731638A/xx unknown
  • 1969-04-17 DE DE19691919592 patent/DE1919592A1/de active Pending
  • 1969-04-17 DE DE19691919604 patent/DE1919604A1/de active Pending
  • 1969-04-21 GB GB1238574D patent/GB1238574A/en not_active Expired
  • 1969-04-21 GB GB1238573D patent/GB1238573A/en not_active Expired
  • 1969-04-21 US US818101A patent/US3677760A/en not_active Expired - Lifetime
  • 1969-04-21 GB GB1238572D patent/GB1238572A/en not_active Expired

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