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
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
  • G03C1/835—Macromolecular substances therefor, e.g. mordants
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment

Definitions

• the light-sensitive material a layer containing a material capable of absorbing the said surplus light.
• an anti-halation layer is provided on the back-side of the support, an anti-halation layer is provided between the support and the light-sensitive photographic layer, or an anti-irradiation dye is incorporated directly into the light-sensitive photographic layer.
• the anti-irradiation or anti-halation layer contains such a light absorber as dye, colloidal silver, colloidal manganese or carbon black.
• the above-mentioned light absorber has influence on photographic emulsion and brings about various drawbacks such as desensitization, increase of fog, etc., when incorporated into a lightsensitive photographic layer or a layer adjacent thereto, though no substantial problem arises when applied to the back-side of support. Accordingly, in case an anti-halation layer containing a dye is provided adjacent to the light-sensitive photographic layer, the dye diffuses into the light-sensitive photographic layer and absorbs even necessary light to desensitizc the photographic layer. Even when a layer containing such a light absorber as colloidal silver or the like is provided adjacent to the photographic emulsion layer, increase of fog, desensitization and the like drawbacks are brought about in the photographic emulsion layer. Accordingly, the light absorber is incorporated into the light-sensitive photographic layer or a layer adjacent thereto only when sharpness is required at the sacrifice of speed, like in the case of, for example, a high resolution lifhtsensitive photographic material.
• the mordant liberates the dye into the treating solution, or the mordant flows into the treating solution without liberation of the captured dye, whereby the adverse effects of the dye on the image after completion can be overcome.
• the use of the mordant results in such advantages that a non-diffusing dye layer can be freely provided in portions where no dye has been able to be used hitherto, and, particularly, an anti-halation layer can be provided in any layer of a multi-layered lightsensitive material.
• the mordant is not only used for the prevention of halation and irradiation but also applicable to such layer as a filter layer and can be used as a carrier for a filter dye.
• the mordant should have an excellent dye-retaining property and should have no detrimental effect on photographic emulsion.
• mordant of this kind there have heretofore been known dialkylamines disclosed in US. Pat. No. 2,326,057 and urea-polyethyleneimine reaction products disclosed in West German Pat. No. 1,095,120. These mordants, however, are not sufficient in dye-retaining property, so that when said mordants are incorporated into layers adjacent to light-sensitive photographic layers, considerable amounts of the dyes supported by the mordants diffuse and migrate into the photographic layers to deteriorate the photographic properties thereof. Further, the said mordants are required to be used in large amounts, so that there are brought about deterioration in photographic properties of photographic layers due to the mordants themselves and deterioration in physical properties and coatability of the resulting light-sensitive films. Thus, there have not yet been obtained mordants capable of satisfying various conditions required for mordants.
• the molar content of N-(l,l-dimethyl- 3-oxobutyl)acrylamide in the starting polymers containing the N-(l,1-dimethyl-3-oxobutyl)acrylamide is desirably at least 30 mole percent
• the molar content of monomer unit having the guanidylketimine structure in the polymers containing the guanidylketimine structure which are obtained by condensation of the aforesaid polymers with aminoguanidine or salts thereof is desirably at least 10 mole percent.
• the N-(1,1-dim ethyl-3-oxobutyl)acrylamide is highly copolymerizable with other vinyl monomers to give optional copolymers.
• the said other vinyl monomers include acrylic acid esters, methacrylic acid esters, acrylamides and derivatives thereof, styrene, vinylpyrrolidone, 2-alkylvinylimid'azole derivatives, and vinyl esters such as, for example, vinyl acetate, vinyl butyrate, vinyl propionate and acrylonitrile.
• monomers containing COl-l and SO,H groups, such as acrylic, methacrylic and methylenesulfonic acids are undesirable for the purpose of the present invention and disturb the dye-retaining property.
• the molecular weights of the polymers having the aforesaid guanidylketimine structure which are used in the present invention are preferably'about 8,500 to 80,000 in view of the compatibility thereof with gelatine, polyvinyl alcohol and the like hydrophilic'colloid layers to which the polymers are applied.
• Typical examples of the polymers having the aforesaid guanidylketimine structure are .set forth below together-with synthesis examples thereof, but polymers usable in the present invention are-not limited thereto.
• the resin was recovered by filtration, washed 2 or more times with 100 cc. of a 40 percent aqueous caustic soda solution and then dissolved in 100 ml. of a 10 percent dilute aqueous hydrochloric acid solution. The resulting solution was subjected to filtration, and the filtrate was poured into a mixture comprising 1 liter of acetone and 10 ml. of sodium chloride water to precipitate a resin.
• This resin was recovered by filtration, dissolved in l50 ml. of ethyl alcohol, filtered and then precipitated in 1 liter of ether. Subsequently, the resin was recovered by filtration, washed with ether and then dried under reduced pressure to obtain 11.4 g. of a yellowish resin, N content 20.95 percent.
• the polymer obtained according to any of the abovementioned synthesis examples may be incorporated into a light-sensitive material in such a manner that an aqueous solution, for example, of said polymer is dispersed in a hydrophilic colloid such as gelatine or polyvinyl alcohol, and the resulting dispersion is charged with a suitable dye and then coated on the support, light-sensitive photographic layer or filter layer of the light-sensitive material.
• aqueous solution of the polymer may have previously been incorporated into the light-sensitive photographic layer.
• the hydrophilic colloid may have been incorporated with such a vehicle as anionic, cationic or amphoteric surface active agent, and with such ordinary photographic additives as hardener, stabilizer, etc. If necessary, the polymer may be used in combination with a known mordant.
• Light-sensitive materials to which the polymer of the present invention is applicable are those containing various silver halides such as silver chloride, silver chlorobromide, silver bromide, silver iodobromide, etc.
• the amount of the polymer to be incorporated into a light-sensitive material varies depending on the kind of the light-sensitive material, the purpose of application and the kind of a layer to which the polymer is applied, but is, in general, 2 to 40 g. per g. of dry gelatin, for example.
• the amount of a dye to be supported by said polymer is preferably 1 to 20 g.
• an acid dye having a sulfone or carboxyl group is particularly preferable. Typical examples of such dye are as follows.
• EXAMPLE 1 To 50 ml. of an aqueous solution containing 3 g. of gelatin and 200 mg. of saponin was added 4 ml. of a 5 percent aqueous solution of the polymer obtained in Synthesis Example 1 of the present invention. Further, 5 ml. of an aqueous solution containing 1 percent of the dye (7) was added thereto. The resulting mixed solution was charged with a given amount of a hardener and then adjusted to pH 6.3, and the total amount of the solution was made 100 ml. to prepare a sample (A). In order to ascertain the effect of the polymer, a sample (B) was prepared in the same manner as above, except that the polymer was not used. Further, acontrol sample was prepared in the same manner as above,except that the polymer and the dye'were not used.
• Metol N-methyl-paminophenol sulfate 3 g. Anhydrous sodium sulfite 50 g. Hydroquinone 6 g. Sodium carbonate (monohydrate) 29.5 g. Potassium bromide l g. Water to make 2 liters TABLE 1 Photographic Photographic speed to speed to Sample blue light green light Fog Sharpness Control 100 100 0.07 (A) 95 82 0.07 Greatly improved (B) 89 42 0.07
• the film sample (A) containing the polymer having the aforesaid guanidylketimine structure was improved in sharpness to the same extent as that of the film sample (B) containing no such polymer, without being increased in fog as compared with the sample (B). According to microscopic observation, it was found that in the case of the film sample (B), the diffusion of dye into the emulsion layer was marked, whereas in the case of the film sample (A), no such diffusion was substantially observed.
• a film sample (C) was prepared in the same manner as above, except that the dye (6) was used in place of the dye (7).
• a film sample (D) was prepared in the same manner as above, except 9 that the polymer was not used.
• the samples (C) and (D) were also measured in photographic speed and sharpness to obtain the results as set forth in Table 2.
• the polymer having the aforesaid guanidylketimine structure was excellent in dye-retaining property and had no' such fear as to bring about any increase of fog, desensitization and the like damages in photographic properties.
• EXAMPLE 2 T o 50 ml. of an aqueous solution containing 4 g. of gelatin and 200 mg. of saponin were added 10 ml. of a 6 percent aqueous solution of the polymer of Synthesis Example 2 and 10 ml. of each of 1 percent aqueous solutions of the exemplified dyes (2), (6) and (8). The resulting mixed solutions were individually charged with a hardener, and then the total amount thereof was made 100 ml. Each of these solutions was coated as a black anti-halation solution on a transparent film bases to a dry coat thickness of 3 [1,. On each of the thus formed films, a panchromatically sensitized silver chlorobromide emulsion was coated to prepare film samples.
• Control film samples were prepared by using dye solutions in the same manner as above, except that the polymer was not used.
• This dye layer not only had no detrimental effect on the red-light sensitivity of the lower red-sensitive emulsion layer but also showed such effect as to cut unnecessary green-light sensitivity to improve and enhance the color sensitivity of the emulsion layer.
• the non-diffusing dye layer showed such effect that it successfully prevented harmful halation to greatly improve the sharpness of the resulting image.
• EXAMPLE 4 Red-sensitive and green-sensitive emulsions containing a coupler were coated on a base. On the resulting layer, there was formed a yellow filter layer by coating thereon a-solution prepared by adding 10 ml. of a 6 percent aqueous solution of the polymer of Synthesis Example 5 and 20 ml. of a 1 percent aqueous solution of the exemplified dye (3) to 60 ml. of an aqueous solution containing 3 g. of gelatin and 200 mg. of saponin. Subsequently, a blue-sensitive emulsion containing a coupler was further coated on the yellow filter layer to obtain a light-sensitive color photographic material.
• the thus obtained color photographic material was subjected to color development and investigated in photographic speed of the blue-sensitive emulsion.
• the filter layer showed such filter characteristic as to successfully cut unnecessary blue light sensitivity of the lower layer. From this also, it is understood that the above-mentioned polymer has firmly bonded even to such a dye as the dye (3), which has only one acid radical. During the course of development, the filter layer was decolored to transparency.
• a light-sensitive silver halide photographic material comprising one or more layers containing an acidic dye and as a mordant a polymer having structural units of the formula wherein X is an acid radical and n is l or 2.

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Citations (2)

• 1970
  • 1970-03-20 JP JP45023142A patent/JPS4915820B1/ja active Pending
• 1971
  • 1971-03-19 US US126327A patent/US3706563A/en not_active Expired - Lifetime
  • 1971-03-19 DE DE19712113381 patent/DE2113381A1/de active Pending
  • 1971-04-19 GB GB1297324D patent/GB1297324A/en not_active Expired

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