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
  • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
  • G03C1/8155—Organic compounds therefor
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/134—Brightener containing

Definitions

• the present invention relates to a color printing paper containing a fluorescent brightening agent and an ultraviolet absorber and more particularly to a color printing paper which has been fluorescent-brightened by incorporating a ballasting or diffusion resistant and water soluble fluorescent brightening agent and which is prevented from being faded and stained by the action of ultraviolet rays due to the incorporation in the printing paper of an ultraviolet absorber.
• a method in which a substituent for improving the dyeing affinity of gelatin is introduced into the gelatin. Subsequently the gelatin is dyed with a fluorescent brightening agent.
• a method is also known in which a compound having a good dyeing aflinity for a fluorescent brightening agent, such as polyvinylpyrrolidone (see Japanese patent publication 7,127/59) or poly-N-vinyl-S- methyl-Z-oxazolidinone (see Japanese patent publication 22,065/64), is dispersed in an aqueous gelatin solution and then the gelatin is dyed with the fluorescent brightening agent.
• loss of the fluorescent brightening agent still occurs and hence the brightening efl'ect is reduced considerably due to photographic processing and washing.
• an ultraviolet absorber in a layer on an emulsion layer or in the emulsion layer to improve the light fastness of a color image formed on the emulsion layer.
• Ultraviolet absorbers usually employed for this purpose mainly absorb ultraviolet rays in the range of from 300 to 400 m. It is also known that use of ultraviolet absorbers absorbing ultraviolet rays of wavelengths as long as possible is effective. However, if the absorption of the ultraviolet absorber extends to wavelengths over 400 my, the compound is yellow in color and has an adverse effect on the whiteness of background. Therefore, it is desirable to apply a fluorescent brightening agent-containing layer on an ultraviolet absorber containing layer to prevent coloring by the ultraviolet absorber aand also to complement the reduced brightening effect by the incorporation of an ultraviolet absorber as mentioned above.
• An object of the present invention is to provide a color photographic printing paper having a sufficient whiteness and for which fading is minimized by the presence of an ultraviolet absorber. That is, the object of the present invention is to provide a color photographic printing paper in which an ultraviolet absorber and a fluorescent brightening agent are employed in which the functions of both can be obtained.
• R and R each represents a halogen atom, -O R, 4R,
• R and R represents a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, a hydroxyalkyl group, a sulfoalkyl group, an alkali metal or an ammonium salt of said sulfoallryl group, a carboxyalkyl group, an alkali metal or an ammonium salt of said carboxyalkyl group, an aralkyl group, an aryl group having from 6 to 18 carbon atoms, a substituted aryl group by a substituent such as a hydroxy group, a carboxyl group, or a sulfonic acid group, an alkali metal or an ammonium salt of said sulfonic acid group, a cycloalkyl group having from 6 to 10 carbon atoms, or a substituted cycloalkyl group;
• A represents an alkylene group having from 4 to carbon atoms or an alkylene group containing a hetero-atom or a hetero-atomic group; and M represents an
• a baryta-containing layer, a blue-sensitive emulsion layer containing a yellow coupler, an intermediate layer, a green-sensitive emulsion layer containing a magenta coupler, an intermediate layer, a red-sensitive emulsion layer containing a cyan coupler, and a protective layer are formed on a support paper in this order.
• an ultraviolet absorber is usually incorporated in an intermediate layer between the cyan coupler-containing emulsion layer and the magenta coupler-containing emulsion layer and a fluorescent brightening agent is incorporated in the protective layer.
• the aforesaid ultraviolet absorber can be dissolved in a high boiling solvent or in a mixture of a low boiling solvent and a high boiling solvent, the resulting solution is dispersed by emulsification in an aqueous gelatin solution, and the dispersion is added in the above-mentioned photographic layer or the ultraviolet absorbent can be added directly to the above-mentioned photographic layer, as a solution, as an alkaline aqueous solution.
• these brightening agents are the high molecular weight fluorescent brightening agents having the following repeating units respectively:
• the high molecular weight flourescent brightening agents suitable for use in the invention are polymeric materials and generally have molecular weights ranging from about 20,000 to 1,000,000. A range of from 100,000 to 400,000 is preferred.
• the amount of the high molecular weight fluorescent brightening agent of the present invention to be incorporated in photographic layer is suitably from 0.5 to mg./ 100 cm. and that of the ultraviolet absorber is usually from 2 to mg./ 100 cm.
• the fluorescent brightening agents known at present also act simultaneously as ultraviolet absorbers.
• the high molecular weight fluorescent brightening agents used in the present inven- Compound tion also have ultraviolet absorbing functions.
• the use of the fluorescent brightening agent results in insuflicient ultraviolet absorbing effect. If the amount of the fluorescent brightening agent is increased to increase the ultraviolet absorbing effect, the density of the color image will be reduced and also the density of yellow component will be reduced.
• the fluorescent brightening agent can be incorporated in the photographic layer by the indirect method or a direct method.
• a conventional fluorescent brightening agent is incorporated in the uppermost photographic layer of a color photographic printing paper by the indirect addition method, the incorporated material is deposited by the application of mechanical impact or rubbing onto the printing paper, otherwise the printing paper becomes sticky or adheres to a sheet of an album on storage.
• the conventional fluorescent brightening agent is employed, it cannot be incorporated in the uppermost layer.
• the fluorescent brightening agent of the present invention can be incorporated in the uppermost layer without the aforesaid drawbacks. This makes it possible to utilize more effectively the function of the agent as fluorescent brightening agent.
• the high molecular compound of the present invention when incorporated in any other photographic layers than the uppermost layer, it also exhibits an ultraviolet absorbing effect and a fluorescent brightening eflect.
• the photographic silver halide emulsions employed in the color photographic printing paper of the present invention are usually gelatino silver halide light-sensitive emulsions.
• a synthetic resin such as polyvinyl alcohol or polyvinyl acetal can be employed in the present invention instead of gelatin.
• the ultraviolet absorber can be incorporated in any layer other than the protective layer, and the high molecular Weight fluorescent brightening agent of the present invention can be incorporated in a layer containing the ultraviolet absorber or in a layer disposed on top of the layer containing the ultraviolet absorber, e.g., the layer containing the ultraviolet absorber lies closer to the support while the layer containing the fluorescent brightening agent lies farther from the support.
• Color photographic printing paper A was composed of a paper support having coated thereon a baryta-containing layer; a blue-sensitive emulsion layer containing a yellow coupler, 3,5 dicarboxy-, -(4-stearoylamidobenzoyl) 1 1 acetanilide; an intermediate layer; a green-sensitive emulsion layer containing a magenta coupler, 1-(3-sulfo-4- phenoxyphenyl)-3-stearoyl-5-pyrazolone; an ultraviolet absorbing layer containing Compound 17, shown above; a red-sensitive emulsion layer containing a cyan coupler, N-n-octadecyl-1-hydroxy-4-sulfo-Z-naphthamide; and a protective layer in this order.
• Color photographic printing paper B had the same layer construction except that the ultraviolet absorbing layer containing Compound 17 was replaced with an intermediate gelatin layer containing no ultraviolet absorber.
• the fluorescent brightening agent of the present invention, Compound 14 was incorporated in each of the seven photographic layers in an amount of 5 mg./ 100 cm. to prepare seven different color printing papers.
• These color photographic printing papers were subjected to conventional color photographic processing and the whiteness of the printing papers thus processed was measured. The results obtained are shown in the following table. The whiteness in the table is shown by the photographic density of the yellow component at the unexposed portions.
• a protective layer at a thickness of 2.0 microns.
• the above protective layer was formed by adding gradually a 4% dimethylformamide-water (1:1) solution of the high molecular weight fluorescent agent of this invention, Compounds 1-16, or known flourescent brightening agents, Compound 26,
• the known fluorescent brightening agents i.e., Compound 26 or Compound 27, were incorporated in the uppermost layers, the compounds diifused out during the photographic processing and the brightening effect was reduced. Also, when the ultraviolet absorber was also employed in the present invention, the color photographic printing paper had an excellent fastness to light.
• a color photographic printing paper comprising a support with multiple photographic layers, at least one of said layers containing an ultraviolet absorber and a fluorescent brightening agent or one of said layers closer to said support containing an ultraviolet absorber and a second layer farther away from said support containing a fluorescent brightening agent, provided that the layer containing said ultraviolet absorber is not a protective layer, said fluorescent brightening agent being a high m0- lecular weight compound having repeating units represented by the general formula:
• R is selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, an aryl group having from 6 to 12 carbon atoms, a hydroxyalkyl group having from 2 to 4 carbon atoms, and a sulfoalkyl group having from 1 to 4 carbon atoms; wherein R and R each are selected from the group consisting of a halogen atom, OR, SR,
• R and R each are selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aralkyl group, an aryl group having from 6 to 18 carbon atoms, a substituted aryl group, or a cycloalkyl group having from 6 to 10 carbon atoms, or a substituted cycloalkyl group; and wherein A is selected from the group consisting of an alkylene group having from 4 to carbon atoms, an alkylene group having a hetero atom and an alkylene group having a hetero atomic group; and M is selected from the group consisting of an alkali metal atom and an ammonium group.
• said ultraviolet absorber is selected from the group consisting of a benztriazole derivative, a benzophenone derivative, a thiazolidone derivative, a cinnamic acid ester, an oxathiazole derivative, a thiazole derivative, an imidazole derivative, an oxadiazole derivative, a thiadiazole derivative, a thiophene, a benzalazine derivative, and a bis-hydroxyarylamide compound.
• a color photographic printing paper which comprises a support having thereon, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, said paper having a layer containing a fluorescent brightening agent on the uppermost silver halide emulsion layer and said uppermost silver halide emulsion layer containing an ultraviolet absorbser, said fluorescent brightening agent being a high molecular weight compound having repeating units of the formula:
• R is selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, an aryl group having from 6 to 12 carbon atoms, a hydroxylalkyl group having from 2 to 4 carbon atoms, and a sulfoalkyl group having from 1 to 4 carbon atoms; wherein R and R each are selected from the group consisting of a halogen atom, OR, SR,
• R wherein R and R each are selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aralkyl group, an aryl group having from 6 to 18 carbon atoms, a substituted aryl group, or a cycloalkyl group having from 6 to 10 carbon atoms, or a substituted cycloalkyl group; and wherein A is selected from the group consisting of an alkylene group having from 4 to 5 carbon atoms, an alkylene group having a hetero atom and an alkylene group having a hetero atomic group; and M is selected from the group consisting of an alkali metal atom and an ammonium group.
• a color photographic printing paper comprising a support having thereon, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, said paper having a layer containing a fluorescent brightening agent on the uppermost silver halide emulsion layer and having a layer containing an ultraviolet absorber between the uppermost silver halide emulsion layer and the middle silver emulsion layer, said fluorescent brightening agent being a high molecular weight compound having repeating units of the formula:
• R is selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, an aryl group having from 6 to 12 carbon atoms, a hydroxyalkyl group having from 2 to 4 carbon atoms, and a sulfoalkyl group having from 1 to 4 carbon atoms; wherein R and R each are selected from the group consisting of a halogen atom, OR, SR,
• R and R each are selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aralkyl group, an aryl group having from 6 to 18 carbon atoms, a substituted aryl group, or a cycloalkyl group having from 6 to 10 carbon atoms, or a substituted cycloalkyl group; and wherein A is selected from the group consisting of an alkylene group having from 4 to 5 carbon atoms, an alkylene group 15 having a hetero atom and an alkylene group having a hetero atomic group; and M is selected from the group consisting of an alkali metal atom and an ammonium group.
• a color photographic printing paper comprising a support with multiple photographic layers, at least one of said layers containing an ultraviolet absorber and a fluorescent brightening agent or one of said layers closer to said support containing an ultraviolet absorber and a second layer farther away from said support containing a fluorescent brightening agent, provided that the layer containing said ultraviolet absorber is not a protective layer, said fluorescent brightening agent being a high molecular weight compound having repeating units of the formula:
• R is selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, an aryl group having from 6 to 12 carbon atoms, a hydroxyalkyl group having from 2 to 4 carbon atoms, and a sulfoalkyl group having from 1 to 4 carbon atoms;
• R and R each are selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aralkyl group, an aryl group having from 6 to 18 carbon atoms, a substituted aryl group, or a cycloalkyl group having from 6 to 10 carbon atoms, or a substituted cycloalkyl group; and wherein A is selected from the group consisting of an alkylene group having from 4 to 5 carbon atoms, an alkylene group having a hetero atom and an alkylene group having a hetero atomic group; and M is selected from the group consisting of an alkali metal atom and an ammonium group,
• said ultraviolet absorber being a member selected from the group consisting of a benztriazole derivative, a :benzophenone derivative, a thiazolidone derivative, a cinnamic acid ester, an oxathiazole derivative, a thiazole derivative, an imidazole derivative, an oxadiazole derivative, a thiadiazole derivative, a thiophene, a benzalazine derivative, and a bis-hydroxyarylamide compound.
• said fluorescent brightening agent is a member selected from the group consisting of:
• the molecular weight of the fluorescent brightening agent ranges from about 20,000 to 1,000,000.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Paper (AREA)
• Laminated Bodies (AREA)

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Cited By (4)

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• 1969
  • 1969-01-08 JP JP44001554A patent/JPS4910696B1/ja active Pending
  • 1969-12-31 FR FR6945623A patent/FR2027903A1/fr not_active Withdrawn
• 1970
  • 1970-01-02 DE DE19702000233 patent/DE2000233A1/de active Pending
  • 1970-01-06 GB GB678/70A patent/GB1263441A/en not_active Expired
  • 1970-01-08 US US1564A patent/US3677762A/en not_active Expired - Lifetime

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