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
  • 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

Definitions

• This invention relates to the hardening of photographic layers, particularly of silver halide emulsion layers which contain as a colloidal carrier material a protein derivative, particularly gelatin.
• Photographic materials are treated with photographic processing solutions which have different pH values and diiferent temperatures. It is, therefore, extremely important to use photographic products with colloidal layers which when compared with pure gelatin are more resistant to water, swell less and have a higher melting point. For this reason, the gelatin layers must be hardened without depriving them of their water permeability.
• a large number of publications have recommended whole series of compounds and classes of compounds as hardening agents.
• Metal salts such as chromium, aluminum or Zirconium salts; aldehydes and halogen containing aldehydes such as formaldehyde, dialdehydes (glyoxal) and mucochloric acid; 1,2 and 1,4-diketones such as cyclohexanedione-l,2; quinone; chlorides of di basic organic acids; dianhydrides of tetracarboxylic acids; compounds with several reactive vinyl group such as vinylsulfone or acrylamide; compounds with at least two easily splitable heterocyclic rings such as ethylene oxide and ethyleneamine; and polyfunctional esters of methanesulfonic acid.
• Metal salts such as chromium, aluminum or Zirconium salts
• aldehydes and halogen containing aldehydes such as formaldehyde, dialdehydes (glyoxal) and mucochloric acid
• 1,2 and 1,4-diketones such as cyclo
• the hardening agents increase the viscosity of the coating solution to an alarming degree.
• Other hardening agents suffer from the disadvantage that they become active only after prolonged storage. In this manner, these hardening agents change the sensitometric characteristics of the layer in an uncontrollable manner. One refers to this effect as after-hardening.
• R R R and R which may be alike or different represent hydrogen or lower alkyl groups such as methyl, ethyl, or propyl; n is a positive integer ranging from 1 to 7; X and X together represent the carbon atoms necessary to complete a fully hydrogenated 5 or 6 membered heterocyclic nucleus such as a piperazine or pyrazolidine; and Y and Y together represent the atoms necessary to complete an aromatic nucleus of the benzene series which may be further substituted by a suitable group such as a carboXy group to increase the water solubility of the hardening agent.
• hardening agents can be readily prepared by reacting in an aqueous alkaline solution, an aliphatic, aromatic or heterocyclic diamine with the chloride of an ot-chlorocarboxylic acid.
• the separation and purification of the reaction products does not offer any difiiculties because the compounds precipitate from the solution and need only to be purified by recrystallizing the precipitate.
• diamines which can be used in the reaction are the following:
• l-iexamethylenediamine 1,2-phenylenediamine 1,4-phenylenediamine Pip erazine Pyrazolidine
• chlorides of a-chlorocarboxylic acids which can be used in the preparation of the novel hardening agents are: a-chloracetyl chloride, oc-ChlOlOPIOPiOIlYl chloride and ct-chlorobutyryl chloride.
• a great advantage of the hardeners of this invention resides in the feature that they will not react with any color formers which are present in multilayer color materials. Consequently, they can also be used in multilayer materials having incorporated in the emulsions color formers which are fast to diffusion.
• the compounds do not only harden the layers but improve the adhesion of the several over-coated layers in multilayer materials.
• the danger of separation of the layers in the wet state during the processing and drying is, therefore, reduced.
• the hardening agents are added to the photographic coating preparations in the form of a solution in a suitable water-miscible organic solvent such as methanol, ethanol, dioxane, dimethylformarnide and the like prior to coating. Neither the viscosity nor the pH of the coating solutions are altered by this technique.
• the amounts of hardening agents added depend on the desired effect. In general, from 1.0 to 20.0 grams of hardening agents per kilogram of dry colloidal carrier material such as gelatin are sufiicient. One thereby obtains layers with high melting points. The action of the hardening starts only after the drying of the layer.
• the action of the hardening agents can be explained on a hypothetical basis by assuming that the a-chlorine atom is rendered more labile by the proximity of the CO group and is readily split off; so that the remaining part of the hardener molecule reacts with the amino group of one or several gelatin molecules as indicated by the following formula:
• the emulsion layers and intermediate layers which are hardened with our novel hardening agents can be coated on all known supports such as glass, paper, cellulose esters or other film forming synthetic polymers.
• the general composition of the coating solutions used for the preparation of these layers does not need to be changed because the adhesion of these layers is not adversely influenced by the hardening. In some cases, the.
• adhesion is even improved through the use of the novel hardening agents.
• sensitizing procedure or other conventional methods of preparing the emulsions can be retained without change.
• the hardening agents described herein can be combined with previously known hardening agents if special efl ects are desired.
• these dye-forming compounds unite with the oxidation products of the developing agent to form an azornethine or indoaniline dye.
• the emulsion layer may be free from color formers in which case the film is processed with the color formers in the color developers by the selective second exposure and color development method as described in US. Patent 1,897,866, 1,900,870, 1,928,709, and 1,980,941.
• Multicolor film in which each element bears a color yielding layer comprising a hydrophilic film-forming synthetic polymer containing a plurality of hydroxyl groups and having a plurality of color components and, in addition, containing light-sensitive silver salts in described in US. Patents 2,397,864, 2,397,865, 2,397,866, and 2,397,867.
• Example I To 1 kilogram of a silver chlorobromide emulsion which is ready for coating and contains about 65 grams of gelatin, there was added 1.5 grams of bis-chloroacetyl- N,N-di1nethylethylenediamine dissolved in methanol. The addition of this hardening mixture does not increase the viscosity and does not change the pH which is preferably kept between a range of 6.0 to 8.0. The emulsion is coated on baryta paper. After the usual drying and storing for 48 hours at a temperature of 45, it was noted that the layer had a melting point of 100 C. The hardening is not influenced by the pH in a pH range of 6.0 to 8.0 and the photographic properties of the emulsions are not changed.
• the coating solution contains as the hardening agent 1.4 grams of bis-chloroacetyl-N,N'-dimethylethylenediamine dissolved in methanol.
• the coated layer is dried and stored for 48 hours after which time it showed a melting point of C. After completed color processing, the layer showed good adhesion to the support and contained a stain-free yellow dye image.
• the photo graphic properties of this emulsion including color density, speed and contrast were the same as those of an unhardened type emulsion.
• Example III The light-sensitive material prepared in accordance with Example II was overcoated with a red-sensitive silver chloride emulsion which contains per 1 liter of solution:
• the coating solution contained 3 grams of the hardening agent bis-chloroacetyl-ethylenediamine. After coating, drying and storage, the melting point of the layer was determined as being above 90 C. The adhesion of the two color emulsion layers was noticeably improved by our hardening agent when compared with conventional hardening agents.
• Example IV A subbed cellulose acetate film support was coated with 1 kilogram of a gelatin solution which contained approximately 30 grams of gelatin together with an antihalation dye and 1 gram of the compound bis-chloroacetyl-1,2- phenylenediamine-4-carboxylic acid dissolved in ethanol. After drying and storage, the backing layer had a melting point above C. This layer showed no tendancy to swell and had a very high resistance to abrasion in its wet state.
• Example V Example IV was repeated with the exception that the hardening agent used was 1 gram of bis-chloroacetyl-N, N'-dimethylhydrazine.
• the backing layer obtained therefrom shows very little swelling and a high abrasion resist ance in the wet state.
• a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing a hardening amount of a bis-chloroacylamido hardening agent selected from the group of compounds having the following general formulae:
• R1OHC o-N-c'n cn-N o o-cn-Ri I 1 -Yr 01 wherein R R R and R are members selected from the group consisting of a hydrogen atom and lower alkyl groups, n represents a positive integer ranging from 1 to 7; X and X represent the carbon atoms necessary to complete a hydrogenated heterocyclic nucleus; and Y and Y represent the carbon atoms necessary to complete an aromatic nucleus of the benzene series.
• a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing a hardening amount of a compound having the following formula:
• a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing a hardening amount of a compound having the following formula:
• a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing a hardening amount of a compound having the following formula:
• a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing in addition to a color former fast to diffusion capable of forming upon development with a primary amine developing agent, a dye image selected from the group consisting of azomethine, indoaniline and phenazonium dye images, a hardening amount of a hardening agent selected from the group of compounds having the following general formulae:
• R R R and R are members selected from the group consisting of a hydrogen atom and lower alkyl groups, n represents a positive integer ranging from 1 to 7; X and X represent the carbon atoms necessary to complete a hydrogenated heterocyclic nucleus; and Y and Y represent the carbon atoms necessary to complete an aromatic nucleus of the benzene series.
• a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing in addition to a color former fast to diffusion capable of forming upon development with a primary amino developing agent, a dye image selected from the group consisting of azomethine, indoaniline and phenazonium dye images, a hardening amount of a hardening agent of the following formula:
• a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing in addition to a color former fast to diffusion capable of forming upon development with a primary amino agent, a dye image selected from the group consisting of azomethine, indoaniline and phenazonium dye images, a hardening amount of a hardening agent of the following formula:
• a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing in addition to a color former fast to diffusion capable of forming upon development with a primary amino development agent, a dye image selected from the group consisting of azomethine, indoaniline and phenazonium dye images, a hardening amount of a hardening agent of the following formula:
• a photo-sensitive element comprising a support and coated thereon a gelatin silver halide emulsion layer and a gelatin layer, at least one of these gelatin layers containing a hardening amount of a bis-chloroacylamido hardening agent selected from the group of compounds having the following general formulae:
• R R R and R are members selected from the group consisting of a hydrogen atom and lower alkyl groups, n represents a positive integer ranging from 1 to 7; X and X represent the carbon atoms necessary to complete a hydrogenated heterocyclic nucleus; and Y and Y represent the carbon atoms necessary to complete an aromatic nucleus of the benzene series.
• a photo-sensitive element comprising a support carrying a gelatin silver halide emulsion and a gelatin layer coated thereon, at least one of these gelatin layers containing a hardening amount of a compound having the following formula:
• a photo-sensitive element comprising a support carrying a gelatin silver halide emulsion and a gelatin layer coated thereon, at least one of these gelatin layers containing a hardening amount of a compound having the following formula:
• a photo-sensitive element comprising a support References fired by the Examiner carrying a gelatin silver halide emulsion and a gelatin UNITED STATES PATENTS layer coated thereon, at least one of these gelatin layers r containing a hardening amount of a compound having the 3/61 Levme 11 FOREIGN PATENTS following formula: 5

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Cited By (5)

Citations (2)

• 0
  • BE BE606194D patent/BE606194A/xx unknown
• 1960
  • 1960-07-16 DE DEA35144A patent/DE1130283B/de active Pending
• 1961
  • 1961-07-13 US US123654A patent/US3174861A/en not_active Expired - Lifetime
  • 1961-07-14 GB GB25649/61A patent/GB932978A/en not_active Expired

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