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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
• • 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
  • G03C5/38—Fixing; Developing-fixing; Hardening-fixing

Definitions

• the invention relates to a process for hardening exposed photographic layers, particularly those photographic layers which contain color couplers, by treating the exposed layers with prehardening baths.
• a process for hardening photographic layers has now "ice been found in which an exposed photographic material which comprises at least one silver halide gelatin emulsion layer which may contain color coupler is treated with a prehardening bath before development, the exposed material being first treated with an aqueous bath at a pH of between 3 and 7 and which contains 0.5 to 10% by weight of a dissolved hardener which at these pH values has little or no hardening effect on gelatin, and additives which inhibit swelling, followed by a second aqueous bath having a pH of between 11 and 14 which also contains additives which inhibit swelling.
• the advantage of the process of the invention is that the step in which diffusion of hardener into the layer occurs is separate from the actual hardening process. Little or no hardening of the photographic layer should take place in the first bath, which contains the hardener. Suitable hardeners for this bath are, therefore, those which have a very low hardening effect at acid pH values of between 3 and 7. In the second, alkaline bath which has a pH value of above 11, the hardener adsorbed in the layer then reacts with the gelatin of the photographic layer.
• Suitable hardeners are therefore quite generally those which have no effect in acid pH ranges but a very rapid hardening effect at alkaline pH values.
• the first class hardeners include eg the following:
• the second class of compounds includes quaternary ammonium salts which can be obtained by reacting the above mentioned compounds with tertiary ammonium salts, e.g. those described in Belgian Pat. No. 740,599 or in British Pat. No. 1,158,263, such as the following:
• Reaction product of compound 6 with diazabicyclooctane hydrochloride (13) Reaction product of compound 2 with N-methylmorpholinium chloride
• suitable are compounds Which contain at least 2 vinylsulfone or acryloyl groups, especially those of the triazine or hydrotriazine series.
• the amount of the hardening agent in the acid or neutral bath can be varied within wide limits. Preferred are concentrations of between 100 and g./l. of the bath.
• Additives which inhibit swelling are added to both the prehardening baths in order to suppress swelling of the exposed photographic layers in these baths.
• Suitable additives for this purpose are in particular neutral salts of alkali metals with strong acids such as sodium sulfate, potassium sulfate, lithium sulfate or sodium phosphate.
• the additives which inhibit swelling are added in such quantities that layers which have been only slightly hardened will not swell by more than about 200%. In general amounts of between 50 and 160 g./l. have proved sulficient.
• the pH of the bath which contains the hardener is adjusted to a value between 3 and 7 with mineral acids and suitable buffer solutions.
• Inorganic acids such as hydrochloric acid or sulfuric acid, sodium acetate or sodium citrate, etc. are suitable for this purpose.
• the baths may, of course, also contain other additives according to the requirements of the particular photographic process, e.g. substances which prevent fogging, such as heterocyclic compounds, e.g. benzotriazole or mercapto substituted heterocyclic compounds, or inorganic salts which have this effect, such as sodium bromide.
• substances which prevent fogging such as heterocyclic compounds, e.g. benzotriazole or mercapto substituted heterocyclic compounds, or inorganic salts which have this effect, such as sodium bromide.
• the second preliminary bath used hereinafter briefiy termed the alkaline bath, consists of an aqueous solution of an additive which prevents swelling, this solution having a pH of between 11 and 14.
• the pH is most simply adjusted by the addition of alkali metal hydroxides.
• Suitable additives for preventing swelling are those mentioned earlier for bath I.
• Buffers and antifog agents may also be added to the alkaline bath as described above.
• the process according to the invention is superior to the known process described earlier particularly in its simplicity.
• the stability of the baths is particularly good. Since the first preliminary bath has only a low pH value, the stability of the usual hardeners is extremely high. The hardening reaction itself proceeds very rapidly in the alkaline bath so that only short treatment times are required.
• the baths used in the process of the invention are inert to the subsequent processing baths, particularly to the development bath. Even if substantial quantities of the alkaline bath are carried over into the developer bath,
• the photographic properties of the layers are in no way influenced by the process according to the invention.
• the process according to the invention is particularly advantageous for processing color photographic materials.
• the photographic properties of the multi-layered materials used for this purpose also remain unchanged. Layers which have exceptionally good mechanical properties are obtained.
• the processing time may vary within wide limits.
• a treatment time of about /2 to 1 minute is generally sufficient in the first preliminary bath which contains the hardener.
• the treatment time in the alkaline bath is about /2 to 3 minutes.
• the temperature of the baths is about 18 to 30 C., preferably about 20 C. Subsequent photographic processing need not be altered in any way and can be carried out with the baths of the usual composition.
• a multilayered color photographic material on a cellulose triacetate layer support comprising a red-sensitive silver halide emulsion layer which contains a cyan coupler, a green-sensitive silver halide emulsion layer which has a magenta coupler and a blue-sensitive silver halide emulsion layer which has a yellow coupler is exposed in a conventional sensitometer and after exposure it is treated with the following baths:
• Preliminary bath II 800 cc. of water 4 g. of sodium hydroxide 154 g. of sodium sulfate made up to 1 liter pH 12.9, reaction time 60 seconds, temperature 20 C.
• the film samples show no detachment of the layers or reticulation after processing.
• the melting points of the layers are above 100 C. (melting point of initial sample 56 C.).
• partial detachment of the layers had already occurred in the developer.
• the samples could not be processed in baths at 40 C.
• the solutions used as preliminary bath have the following composition:
• Hardener Process A Process B The table shows that no hardening occurs in preliminary bath I with the compounds used. The bath only serves to introduce the hardener into the layer. Hardening takes place in the alkaline preliminary bath II.
• a process for hardening photographic layers by treating an exposed photographic material comprising at least one silver halide gelatin emulsion layer with a preliminary hardening bath followed by development, the improvement consisting of exposing the photographic material containing the silver halide gelatin emulsion layer, treating the exposed material with an aqueous bath which has a pH of between 3 and 7 containing additives which inhibit swelling and containing in hardening concentration of 0.5 to 10% by weight a non-polymeric diifusible organic compound having a relatively lesser hardening effect on the gelatin emulsion layer in a solution at a pH of between 3 and 7 than at a pH between 11 and 14 and immediately follow by subsequently treating the exposed material with a second aqueous bath which has a pH of between 11 and 14 and which also contains additives which inhibit swelling.
• baths contain, as additives which inhibit swelling, neutral salts of alkali metals with strong inorganic acids in such quantities that the swelling of only slightly hardened layers is not more than 2.00%.

Landscapes

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

Applications Claiming Priority (1)

Publications (1)

Family

ID=5743410

Family Applications (1)

Country Status (5)

Cited By (9)

Families Citing this family (1)

• 0
  • BE BE754789D patent/BE754789A/nl unknown
• 1969
  • 1969-08-21 DE DE19691942562 patent/DE1942562A1/de active Pending
• 1970
  • 1970-08-05 GB GB2772670*[A patent/GB1315557A/en not_active Expired
  • 1970-08-05 US US61403A patent/US3676143A/en not_active Expired - Lifetime
  • 1970-08-21 FR FR7030782A patent/FR2059107A5/fr not_active Expired

Also Published As

Similar Documents